US5543518A - Red-shifted tris-aryl-s-triazines and compositions stabilized therewith - Google Patents

Red-shifted tris-aryl-s-triazines and compositions stabilized therewith Download PDF

Info

Publication number
US5543518A
US5543518A US08463140 US46314095A US5543518A US 5543518 A US5543518 A US 5543518A US 08463140 US08463140 US 08463140 US 46314095 A US46314095 A US 46314095A US 5543518 A US5543518 A US 5543518A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
bis
tert
triazine
example
di
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US08463140
Inventor
Tyler A. Stevenson
Ramanathan Ravichandran
Mark S. Holt
Thuy N. Phan
Jean-Luc Birbaum
Vien V. Toan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ciba-Geigy Corp
Original Assignee
Ciba-Geigy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D251/00Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines

Abstract

Tris-aryl-s-triazines which contain from one to three resorcinol derived moieties with at least one of said moieties substituted at the 5-position with an alkyl, phenylalkyl, halogen, thio or sulfonyl group have UV spectra which are red-shifted to the near UV range and provide excellent stabilization to polymeric substrates against the deleterious effects of actinic light.

Description

This is a Divisional of Ser. No. 08/281,381, filed Jul. 27, 1994, pending.

The instant invention pertains to novel red-shifted tris-aryl-s-triazines and their use in protecting polymer systems prone to degradation caused by actinic radiation.

BACKGROUND OF THE INVENTION

Tris-aryl-s-triazines in which at least one of the aryl groups has an hydroxy group ortho to the point of attachment to the triazine ring are well known UV absorbers. It is also well-known that this class of triazines protect organic polymers from the deleterious effects of exposure to actinic radiation.

For the purposes of this application 2,4-dihydroxyphenyl groups on a s-triazine ring may be referred to as resorcinol groups. The numbering system used on the resorcinol group is outlined as follows: ##STR1##

U.S. Pat. Nos. 3,118,887 and 3,268,474 describe the protection of plastic and resinous compositions from UV light by the incorporation of one or more compounds of the class of tris-aryl-s-triazines. The former patent claims 2,4,6-tris-(2,4-dihydroxyphenyl)-s-triazine and 2,4,6-tris-(2-hydroxy-4-alkoxyphenyl)-s-triazines. A tris-5-alkylresorcinol-s-triazine is prepared, but not tested or claimed.

U.S. Pat. No. 3,268,474 claims the composition of a polymeric material and a tris-aryl-s-triazine that has at least one ortho-hydroxyphenyl group and which may be further substituted on each of the three aryl rings by alkyl, alkoxy, halo, etc., with a total of up to three substituents on each ring. Preferred substitution patterns are not given. There are specific claims for compositions including tris-(2-hydroxy-4-alkoxyphenyl)-s-triazines and 2,4-bis-(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine. Again, an example of a tris-alkylresorcinol-s-triazine is given, but it is not tested and its composition with a polymer is not claimed.

U.S. Pat. No. 3,242,175 claims bis-resorcinol-tris-aryl-s-triazines with no substitution on the resorcinol rings. U.S. Pat. No. 3,244,708 claims mono-, bis-, or tris-resorcinol-tris-aryl-s-triazines with no substitution on the resorcinol rings. A Markush structure in the introduction of the patent does refer to mono-resorcinol-tris-aryl-s-triazines that may be further substituted on the resorcinol ring by one or two or combinations of hydroxy, halogen, alkyl, alkoxy, phenyl, or phenylalkyl. Preferred substitution patterns are not mentioned and no such compounds are synthesized or tested.

U.S. Pat. Nos. 4,619,956 and 4,740,542 disclose the use of synergistic amounts of tris-aryl-s-triazines and hindered amine light stabilizers in polymer film coatings or molded articles against the action of light, moisture and oxygen. The tris-aryl-s-triazines referred to in these patents are those described in U.S. Pat. No. 3,268,474. The preferred s-triazine is 4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine or 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine-A Markush structure in the patents describes tris-aryl-s-triazines with at least one hydroxy group ortho to the point of attachment to the triazine ring and which may have up to three substituents on each of the three aryl rings. These substituents include alkyl, alkoxy, halo, etc. Preferred substitution patterns are not given and no compounds with substitution on a resorcinol ring are prepared or tested.

E.P. Application No. 444,323 claims highly-soluble tris-aryl-s-triazines, the process for their preparation, and tbeir composition with an organic solvent. A specific triazine mentioned as useful in this process is 2-(2,4-dihydroxyphenyl)-4,6-bis-(2-dimethylphenyl)-s-triazine. The tris-aryl-s-triazines claimed in this application are based on those described in U.S. Pat. No. 3,268,474. The preferred triazines are mono-resorcinol-tris-aryl based s-triazines. The preferred Markush group shows that the resorcinol ring may be further substituted in the 5-position with alkyl groups. However, the effects of substitution in this position are not mentioned, and no such compounds are prepared or tested.

E.P. Application No. 483,488 claims the synergistic stabilizer composition comprised of a tris-aryl-s-triazine and a hindered amine and the method of stabilizing a polymer by incorporating such a composition. Again, the triazines claimed in the compositions are based on those described in U.S. Pat. No. 3,268,474. The preferred triazines are bis-xylyl-resorcinol based s-triazines. The body of the application does show a Markush structure of a mono-resorcinol-tris-aryl based s-triazine that may be further substituted in the 5-position of the resorcinol ring with alkyl groups. However, no triazines with such further substitution on the resorcinol ring are prepared or tested.

U.S. Pat. Nos. 4,826,978 and 4,962,142 disclose a class of tris-aryl-s-triazines useful as ultraviolet screens for polymers, including coatings. The triazines are based on bis-resorcinol-phenyl-s-triazines with electron withdrawing groups substituted on the phenyl group. No further substitution on the resorcinol groups are referred to.

U.S. Pat. No. 5,106,891 claims coating compositions which contain, as the UV absorber, a mixture of at least one 2-hydroxyphenylbenzOtriazole and at least one 2-hydroxyphenyltriazine. The triazines described are based on mono-resorcinol-tris-aryl-s-triazines, with the preferred structure based on bis-xylyl-resorcinol-s-triazine. The Markush structure discloses that the aryl groups may be substituted by up to three hydroxyl, halogenomethyl, alkyl, alkoxy or halogen, or combinations thereof. Structures are disclosed, therefore, of tris-aryl-s-triazines with substituted resorcinol groups, but preferred substitution patterns are not disclosed, and no such compounds are prepared or tested.

E.P. Application No. 434,608 claims an organic material which has been stabilized against damage by light, heat and oxygen and which contains a combination of a hindered amine and an o-hydroxyphenyl-s-triazine or said triazine alone, the process for stabilizing an organic material by incorporation of the combination of a hindered amine and said triazine or triazine alone, novel o-hydroxyphenyl-s-triazines, and the use of novel s-triazines as a stabilizer for organic materials. Organic materials specifically mentioned are coating binders and radiation-curable coating materials. The preferred triazines are mono-resorcinol-tris-aryl based s-triazines with no further substitution on the resorcinol ring. A Markush structure is claimed that covers tris-aryl-s-triazines with one or two alkyl- or halo-substituted resorcinol groups. Preferred substitution patterns are not given, and no compounds with substituted resorcinol rings are prepared or tested.

E.P. Application No. 442,847 claims a coating composition that contains a binder, a hardening agent, and a tris-aryl-s-triazine as a stabilizer against damage by light, heat, and oxygen. Specifically mentioned is the use of this composition for automobile coatings. Preferred triazines for use in this composition are mono-resorcinol-tris-aryl based s-triazines with no substitution on the resorcinol ring. A Markush structure is described in the claim section that includes tris-aryl-s-triazines with one or two resorcinol groups that may be further substituted by alkyl or halogen. Preferred substitution patterns are not given, and no compounds with substituted resorcinol rings are prepared or tested.

Copending application Ser. No. 08/189,627 claims a polymer film composition which comprises an electro coat primer, a color coat in adhesion to the electro coat, a clear coat in adhesion to the color coat, and a tris-aryl-s-triazine UV absorber in either the color coat or clear coat or both. It is pointed out that a particular subgenus of tris-aryl-s-triazines, those based on bis- and tris-resorcinol-tris-aryl-s-triazines are especially effective in stabilizing such a coating system. A Markush structure in the composition claims describes bis- and tris-resorcinol-tris-aryl-s-triazines that may be substituted on the resorcinol rings by an alkyl of 1 to 6 carbon atoms. Specific substitution patterns are not discussed. An example of the preparation of 2,4,6-tris-(2,4-dihydroxy-5-hexylphenyl)-s -triazine is given, but this compound is not tested.

U.S. Pat. No. 5,298,067 claims a coating material stabilized with monomers or dimers of mono-resorcinol-tris-aryl based s-triazines alone or in combination with a hindered amine or an hydroxyphenylbenzotriazole, and the method of stabilizing a coating material by incorporating these s-triazines. No further substitution on the resorcinol groups is referred to. A coating material specifically mentioned is an automotive laquer.

E.P. Application No. 165,608 discloses s-triazines including a class of tris-aryl-s-triazines, the process for their preparation, and their method of use as UV absorbers in organic materials, especially color photographic materials. Tris-aryl-s-triazines disclosed include those with one to three resorcinol groups that may be substituted with alkyl, alkoxy, hydroxy, or alkyl or phenylcarbonyl. Preferred substitution patterns are not disclosed. Examples are given for bis-resorcinol-tris-aryl-s-triazines with the resorcinol substituted in the 3-position by methyl, in the 6-position by hydroxy, methoxy, and methyl, and in the 5-position by acetyl.

U.S. Pat. No. 3,843,371 claims photographic material which contains a tris-aryl-s-triazine as a stabilizer against UV radiation. A Markush structure in the claims of this patent includes bis-resorcinol-tris-aryl-s-triazines that may have an alkyl substituent in the 6-position of one of the resorcinol rings. Preferred triazines are bis-resorcinol-tris-aryl based s-triazines with no further substitution on the resorcinol rings. A Markush structure in the body of the patent describes tris-aryl-s-triazines that may have one or two resorcinol groups that may be substituted with halogen, hydroxyl, alkyl, alkoxy, phenyl, phenoxy, cycloalkoxy, etc. Preferred substitution patterns are not discussed and no compounds with substituted resorcinol groups are prepared or tested.

E.P. Application No. 468,921 claims aqueous dispersions of s-triazines with at least one anionic or non-ionic compound. The Markush structure in the claim section includes tris-aryl-s-triazines possibly having one resorcinol ring substituted by alkyl or halogen. The substitution pattern is not specified. The preferred triazines include mono-resorcinol-tris-aryl based s-triazines with no substitution on the resorcinol ring and are the only s-triazines exemplified. U.S. Pat. No. 4,831,068 claims a process for stabilizing dyeings on polyester fiber materials with a s-triazine UV absorber and the polyester fiber material treated by such a process. The Markush structure and preferred triazines are the same as in E.P. Application No. 468,921. Again, only s-triazines of the preferred type are shown in the examples.

U.S. Pat. No. 4,950,304 claims the process of quenching or suppressing the fluorescence of natural or synthetic polyamide substrates treated with whitening agents. The process comprises applying to said substrates a liquor containing an hydroxyphenyl-benzotriazole or an hydroxyphenyltriazine and fixing said UV absorber thereon. The Markush structure of s-triazines disclosed includes tris-aryl-s-triazines that may have a substituted resorcinol group. The resorcinol group may be substituted in the 3- or 5-position by halogen, alkyl, cycloalkyl, phenylalkyl, sulfo, etc. Preferred triazine structures are bis-phenyl-resorcinol-s-triazines with a sulfonate group substituted in the 5-position of the resorcinol ring. No s-triazines with resorcinol groups substituted with any of the other substituents are prepared or tested. The advantage of substitution in the 5-position over the 3-position of resorcinol is not discussed.

U.S. Pat. No. 5,096,489 claims a method of stabilizing an ink jet print with the use of an aqueous solution of a dye in combination with a s-triazine. A Markush structure describes tris-aryl-s-triazines that may have one or more resorcinol groups substituted in the 5-position by a sulfo, halo, or alkyl group. The preferred triazines for use in this method are based on his- and tris-resorcinol-tris-aryl-s-triazines with no substitution on the resorcinol rings. No s-triazines with substituted resorcinol groups are exemplified. Advantages of substitution in the 5-position of the resorcinol ring are not discussed.

Tris-aryl-s-triazines containing a 2,4-dihydroxyphenyl (resorcinol) group are well-known ultraviolet screening agents for the protection of organic materials. A drawback to commonly used hydroxyphenyl-tris-aryl-s-triazines is that they cover less of the near-UV spectrum than other commercially available UV absorbers, i.e. hydroxyphenylbenzotriazoles. A welcome addition to the art therefore, would be to provide tris-aryl-s-triazines that cover more of the near-UV spectrum. This invention discloses novel tris-aryl-resorcinol based s-triazines that have significant absorbance in the range of 360-400 nm.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention pertains to novel tris-aryl-s-triazines which contain at least one, and preferably one, 2,4-dihydroxyphenyl (resorcinol aryl) group substituted in the 5-position with a carbon, halogen, thio, sulfinyl or sulfonyl moiety.

More particularly, the instant invention relates to the compounds of formula I, II, III, IV or V ##STR2## where in the compounds of formula I

X and Y are the same or different and are phenyl or phenyl substituted with one to three lower alkyl, halogen, hydroxy or alkoxy;

R1 is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, halogen, --SR3, --SOR3, or --SO2 R3 ; or said alkyl or cycloalkyl substituted by one to eight halogen, --R4, --OR5, --N(R5)2, =NR5, =O, --CON(R5)2, --COR5, --COOR5, --OCOR5 , --CN, --NO2, --SR5, --SOR5, --SO2 R5, --P(O)(OR5)2, morpholinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, piperazinyl or N-methylpiperazinyl groups or combinations thereof; or said alkyl or cycloalkyl interrupted by one to six phenylene, --O--, --NR5 --, --CONR5 --, --COO--, --OCO--, --C(R5)=C(R5)--or --CO--groups or combinations thereof; or said alkyl or cycloalkyl both substituted and interrupted by combinations of the groups mentioned above;

R3 is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms;

R4 is aryl of 6 to 10 carbon atoms, or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; or phenylalkyl of 7 to 15 carbon atoms, or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; or straight or branched chain alkenyl of 2 to 18 carbon atoms;

R5 is defined as R4, or R5 is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms; or R5 is a group of the formula ##STR3## where T is hydrogen, oxyl, hydroxyl, alkyl of 1 to 12 carbon atoms, said alkyl substituted by at least one hydroxyl or lower alkoxy, benzyl or alkanoyl of 2 to 18 carbon atoms;

R2 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl or cycloalkyl substituted by one to eight halogen, epoxy, glycidyloxy, furyloxy, --R4, --OR5, --N(R5)2, --CON(R5)2, --COR5, --COOR 5, --OCOR5, --OCOC(R5)=C(R5)2, --C(R5)=CCOOR5, --CN, --NCO, or ##STR4## or combinations thereof; or said alkyl or cycloalkyI interrupted by one to six epoxy, --O--, --NR5 --, --CONR5 --, --COO--, --OCO--, --CO--, --C(R5)=C(R5)COO--, --OCOC(R5) =C(R5)--, --(R5)C=C(R5)--, phenylene, or -phenylene-G-phenylene in which G is --O--,--S--, --SO2 --, --CH2 --, or --C(CH3)2 --, or combinations thereof; or said alkyl or cycloalkyl both substituted and interrupted by combinations of the groups mentioned above; or R2 is --SO2 R3, or --COR6 ;

R6 is straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, phenyl, alkoxy of 1 to 12 carbon atoms, phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbon atoms or a group --R7 COOH or --NH--R8 --NCO;

R7 is alkylene of 2 to 14 carbon atoms or o-phenylene;

R8 is alkylene of 2 to 10 carbon atoms, phenylene, tolylene, diphenylenemethane or a group ##STR5## with the proviso that when R2 is hydrogen and R1 is n-hexyl, X and Y are not each 5-n-hexyl-2,4-dihydroxyphenyl;

for the compounds of formula II:

X is phenyl or phenyl substituted with one to three lower alkyl, halogen, hydroxy or alkoxy;

R1 and R1 ' are the same or different and are defined as R1 above;

R2 and R2 ' are the same or different and are defined as R2 above; and

with the proviso that when R1 and R1 ' are each n-hexyl, and R2 and R2 ' are each hydrogen, X is not 5-n-hexyl-2,4-dihydroxyphenyl;

for the compounds of formula III:

R1, R1 ' and R1 " are the same or different and are as defined for R1 above;

R2, R2 ' and R2 " are the same or different and are as defined for R2 above; and

with the proviso than when R2, R2 ' and R2 " are each hydrogen, R1, R1 ' and R1 " are not each n-hexyl;

for the compound of formula IV:

X, X', Y and Y' are the same or different and are phenyl, phenyl substituted by one to three lower alkyl, halogen, hydroxy or alkoxy;

L is straight or branched chain alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, alkylene substituted by or interrupted by cyclohexylene or phenylene, or L is --S--, --S--S--, --S--E--S--, --SO--, --SO2 --, --SO--E--SO--, --SO2 --E --SO2 --, --CH2 --NH--E--NH--CH2 --or ##STR6## where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or alkylene interrupted or terminated by cyclohexylene of 8 to 12 carbon atoms;

R2 and R2 ' are the same or different and are defined as R2 is above; and for the compounds of formula V:

X, Y, and R1 are defined as above;

n =2 to 4;

when n=2, Q is straight or branched chain alkylene of 2 to 16 carbon atoms; or said alkylene substituted by one to eight --OH; or said alkylene interrapted by one to eight --CH=CH--or --O--; or said alkylene both substituted and interrupted by combinations of the groups mentioned above; or Q is xylylene or a group --CONH--R8 --NHCO--, --CH2 CH(OH)CH2 O--R9 --OCH2 CH(OH)CH2 --, --CO--R10 --CO--, or --(CH2)m--COO--R11 --OOC--(CH2)m--,

where m=1 to 3; or Q is ##STR7##

R8 is defined as above;

R9 is alkylene of 2 to 50 carbon atoms; or said alkylene interrupted by 1 to 10 --O--, phenylene, or a group -phenylene-G-phenylene- in which G is --O--, --S--, --SO2 --, --CH2 --, or --C(CH2)2 --;

R10 is alkylene of 2 to 10 carbon atoms, or said alkylene interrupted by 1 to 4 --O--, --S--, or --CH=CH--; or R10 is arylene of 6 to 12 carbon atoms;

R11 is alkylene of 4 to 20 carbon atoms, or said alkylene interrupted by 1 to 8 --O--;

when n=3, Q is a group --[(CH2)m COO]3 --R12 where m=1 to 3 and R12 is an alkanetriyl of 3 to 12 carbon atoms;

when n=4, Q is a group --[(CH2)m COO]4 --R13 where m=1 to 3 and R13 is an alkanetetryl of 4 to 12 carbon atoms.

Preferably, the invention pertains to compounds of formula I where X and Y are phenyl or phenyl substituted with one to three lower alkyl or halogen;

R1 is straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, or phenylalkyl of 7 to 15 carbon atoms;

R2 is straight or branched chain alkyl of 2 to 24 carbon atoms, or said alkyl substituted by one or two --OR5, where R5 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, or phenyl; especially where said alkyl is substituted by one hydroxyl and by one --OR5 where R5 is alkyl of 1 to 24 carbon atoms or phenyl;

or compounds of formula IV where X, X', Y and Y' are phenyl or phenyl substituted with one to three lower alkyl or halogen;

R2 and R2 ' are the same or different and are defined as R2 is above;

and L is: ##STR8##

Most preferably, the invention pertains to compounds of formula I where X and Y are phenyl, 2,4--dimethylphenyl, 4-methyl phenyl, or 4-chlorophenyl;

R1 is straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, or phenylalkyl of 7 to 15 carbon atoms;

R2 is straight or branched chain alkyl of 2 to 6 carbon atoms, or said alkyl substituted by one or two --OR5 where R5 is hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms; especially where said alkyl is substituted by one hydroxyl and by one alkoxy of 1 to 24 carbon atoms.

Some examples of preferred compounds of the instant invention are listed below.

a. 4,6-bis-(2,4-dimethylphenyl)-2-[4-(3-dodecyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-s-triazine;

b. 2-[5-hexyl-2-hydroxy-4-(2-hydroxy-3-nonyloxypropoxy)phenyl]-4,6-bis-phenyl-s-triazine;

c. 4,6-bis-(2,4-dimethylphenyl)-2-[2-hydroxy-4-(2-hydroxy-3-nonyloxy-propoxy)-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine;

d. 2-[2-hydroxy-4-octyloxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-phenyl-s-triazine; and

e. 4,6-bis-(2,4-dimethylphenyl)-2-[2-hydroxy-4-hexyloxy-5-(1-methyl-1-phenyl-ethyl) phenyl]-s-triazine.

When any of the groups designated in the formulas is alkyl, such alkyl groups are, for example, methyl, ethyl, isopropyl, n-butyl, tert-butyl, tert-amyl, 2-ethylhexyl, n-octyl, n-undecyl, lauryl, n-heptadecyl and n-octadecyl; when alkylene, such alkylene groups are, for example, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene and 2,2-dimethylpropane-1,3-diyl; when cycloalkylene, such cycloalkylene groups are, for example, cyclopentylene or cyclohexylene; when phenyl substituted by alkyl or alkoxy, such groups are, for example, tolyl, xylyl or methoxyphenyl; when cycloalkyl, such groups are, for example, cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl; when phenylalkyl, such groups are, for example, benzyl, a-phenethyl, 2-phenethyl or 4-tert-butylbenzyl; or when alkyl which are interrupted by --O--or --NR5 --and can be substituted by OH are, for example, methoxyethyl, ethoxyethyl, butoxyethyl, butoxypropyl, CH3 OCH2 CH2 OCH2 CH2 --, CH3 CH2 OCH2 CH2 OCH2 CH2 --, C4 H9 OCH2 CH2 OCH2 CH2 --, dodecyloxypropyl, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, --CH2 CH2 --NH--C4 H9, --CH2 CH2 CH2 NH--C8 H17, --CH2 CH2 CH2 --N(CH3)--CH2 CH(C2 H5)C4 H9, 2-hydroxy-3-nonyloxypropoxy and 2-hydroxy-3-dodecyloxypropoxy.

Another feature of this invention are the processes by which these products may be obtained. The construction of the tris-aryl-s-triazine nucleus is well known and is described in U.S. Pat. Nos. 3,268,474 and 3,244,708. What is claimed here are the processes by which a resorcinol group of a tris-aryl-s-triazine may be "post-alkylated," that is, functionalized by substitution in the 5-position with a saturated carbon.

The intermediates and reagents required to make the instant compounds are largely items of commerce or can be obtained by methods known in the art.

Numerous processes may be employed for this "alkylation". Friedel--Crafts alkylations with alkenes, alkyl halides or alcohols using the appropriate catalyst, e.g. aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, etc.; reduction of the product of a Friedel--Crafts acylation; metal-phenoxide additions across activated (Michael) or unactivated alkenes, with appropriate counterions being potassium, sodium, aluminum, titanium, etc.

The processes preferably employed are Friedel--Crafts alkylations with alkenes using catalytic amounts of p-toluenesulfonic acid or methanesulfonic acid; or aluminum phenoxide additions across unactivated alkenes using catalytic amounts of diisobutyl-aluminum hydride or aluminum isopropoxide.

The process most preferably employed is the aluminum phenoxide addition of the resorcinol-tris-aryl-s-triazine across an unactivated alkene using catalytic aluminum isopropoxide, the reaction being run neat at temperatures between 110° and 250° C. The process is outlined below: ##STR9##

The process for making the instant compounds is preferably run with a two to ten excess equivalent amount of alkene, cycloalkene or phenylalkene compared to the amount of the compound of formula A ##STR10##

Still another aspect of the instant invention is a composition stabilized against the deleterious effects of actinic radiation which comprises

(a) an organic material subject to degradation when exposed to actinic radiation, and

(b) an effective stabilizing amount of a compound of formula I, II, III, IV or V.

The organic material is preferably a polymer, especially a high solids thermoset acrylic/melamine resin or an acrylic urethane resin; most preferably a high solids thermoset acrylic/melamine resin.

Preferably, the composition is a polymer film compositions which comprises

(a) an electro coat primer in adhesion to a metal substrate,

(b) a base or color coat that is in adhesion to the electro coat and which comprises a film-forming binder and an organic pigment or an inorganic pigment or mixtures thereof,

(c) a clear coat that is in adhesion to the base coat and which comprises a film-forming binder, and

(d) an effective stabilizing amount, of at least one tris-aryl-s-triazine UV absorber contained in either the base coat or the clear coat or both base coat and clear coat.

The composition above contains as component (d) between 1 and 20% by weight of the film-forming binder.

Component (d) is preferably incorporated into the base coat.

The instant invention also pertains to the defined above which additionally contains an effective stabilizing amount of at least one 2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; or hindered amine or mixtures thereof.

Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from the group consisting of

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-octylphenyl]-2H-benzotriazole;

2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H -benzotriazole; and

2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.

Preferably, the other tris-aryl-s-triazine is selected from the group consisting of

2,4-bis (2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine; and

2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)-phenyl]-s-triazine.

The alkyd resin lacquers which can be stabilized against the action of light and moisture in accordance with the instant invention are the conventional stoving lacquers which are used in particular for coating automobiles (automobile finishing lacquers), for example lacquers based on alkyd/melamine resins and alkyd/acrylic/melamine resins (see H. Wagner and H. F. Sarx, "Lackkunstharze" (1977), pages 99-123). Other crosslinking agents include glycouril resins, blocked isocyanates or epoxy resins.

The lacquers stabilized in accordance with the invention are suitable both for metal finish coatings and solid shade finishes, especially in the case of retouching finishes, as well as various coil coating applications. The lacquers stabilized in accordance with the invention are preferably applied in the conventional manner by two methods, either by the single-coat method or by the two-coat method. In the latter method, the pigment-containing base coat is applied first and then a covering coat of clear lacquer over it.

It is also to be noted that the compounds of the present invention are applicable for use in non-acid catalyzed thermoset resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicon, isocyanates or isocyanurates. The epoxy and epoxy-polyester resins are crosslinked with conventional crosslinkers such as acids, acid anhydrides, amines and the like. Correspondingly, the epoxide may be utilized as the crosslinking agent for various acrylic or polyester resin systems that have been modified by the presence of reactive groups on the backbone structure.

When used in two-coat finishes, the compounds of the instant invention can be incorporated in the clear coat or both in the clear coat and in the pigmented base coat.

To attain maximum light stabilization, the concurrent use of other conventional light stabilizers can be advantageous. Examples of such stabilizers are UV absorbers of the benzophenone, benzotriazole, s-triazine, cyanoacrylate or oxanilide type, or metal-containing light stabilizers, for example, organic nickel compounds, or hindered amine light stabilizers. In two-coat systems, these additional light stabilizers can be added to the clear coat or both in the clear coat and in the pigments base coat.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polyethylene (which optionally can be crosslinked), polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene.

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene.

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as, for example, ethylene/propylene, propylene/butene-1, propylene/isobutylene, ethylene/butene-1, propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates, ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene.

4. Polystyrene, poly-(α-methylstyrene).

5. Copolymers of styrene or methylstyrene with dienes or acrylic derivatives, such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/ethyl methacrylate, styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block polymers of styrene, such as, for example, styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene, such as, for example, styrene on polybutadiene, styrene and acrylonitrile on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylonitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 5), for instance the copolymer mixtures known as ABS-, MBS-, ASA- or AES-polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrin homo- and copolymers, polymers from halogen-containing vinyl compounds, as for example, polyvinylchloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, as for example, vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate, vinylidene chloride/vinyl acetate copolymers, or vinyl fluoride/vinyl ether copolymers.

8. Polymers which are derived from α,β-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polyacrylamide and polyacrylonitrile.

9. Copolymers from the monomers mentioned under 8) with each other or with other unsaturated monomers, such as, for instance, acrylonitrile/butadiene, acrylonitrile/alkyl acrylate, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halogenide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

10. Polymers which are derived from unsaturated alcohols and amines, or acyl derivatives thereof or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as comonomer.

13. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with polystyrene.

14. Polyurethanes which are derived from polyethers, polyesters or polybutadienes with terminal hydroxyl groups on the one side and aliphatic or aromatic polyisocyanates on the other side, as well as precursors thereof (polyisocyanates, polyols or prepolymers).

15. Polyamides and copolyamides which are derived from aliamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, poly-2,4,4-trimethylhexamethylene terephthalamide, poly-p-phenylene terephthalamide or poly-m-phenylene isophthalamide, as well as copolymers thereof with polyethers, such as for instance with polyethylene glycol, polypropylene glycol or polytetramethylene glycols.

16. Polyureas, polyimides and polyamide-imides.

17. Polyesters which are derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate, poly-[2,2-(4-hydroxyphenyl)-propane]terephthalate and polyhydroxybenzoates as well as block-copolyether-esters derived from polyethers having hydroxyl end groups.

18. Polycarbonates.

19. Polysulfones, polyethersulfones and polyetherketones.

20. Crosslinked polymers which are derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.

23. Thermosetting acrylic resins, derived from substituted acrylic esters, such as epoxy-acrylates, urethane-acrylates or polyester acrylates.

24. Alkyd resins, polyester resins or acrylate resins in admixture with melamine resins, urea resins, polyisocyanates or epoxide resins as crosslinking agents.

25. Crosslinked epoxide resins which are derived from polyepoxides, for example from bis-glycidyl ethers or from cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, rubber, gelatin and derivatives thereof which are chemically modified in a polymer homologous manner, such as cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers, such as methyl cellulose.

27. Mixtures of polymers as mentioned above, for example PP/EPDM, Polyamide 6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS.

28. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, which materials may be used as plasticizers for polymers or as textile spinning oils, as well as aqueous emulsions of such materials.

29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.

30. Polysiloxanes such as the soft, hydrophilic polysiloxanes described, for example, in U.S. Pat. No. 4,259,467; and the hard polyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

31. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins. The unsaturated acrylic resins include the urethane acrylates, polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups and the acylated melamines. The polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst.

32. Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.

33. Epoxymelamine resins such as light-stable epoxy resins crosslinked by an epoxy functional coetherified high solids melamine resin such as LSE-4103 (Monsanto).

In general, the compounds of the present invention are employed from about 1 to about 20% by weight of the stabilized composition, although this will vary with the particular substrate and application. An advantageous range is from 1 to 5%; preferably 1.5 to 2.5%.

The resulting stabilized compositions of the instant invention may optionally also contain from about 0.01 to about 5%, preferably from about 0.025 to about 2%, and especially from about 0.1 to about 1% by weight of various conventional additives, such as the materials listed below, or mixtures thereof.

Other compositions of special interest include those which additionally contain a UV absorber selected from the group consisting of the benzophenones, benzotriazoles, cyanoacrylic acid derivatives, hydroxyaryl-s-triazines, organic nickel compounds and oxanilides.

Preferred UV absorbers are selected from the group consisting of 2-[2-hydroxy-3,5-di-(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5octylphenyl]-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(ω-hydroxy-octa(ethyleneoxy)carbonyl)ethylphenyl]-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-octyloxycarbonylethyl)phenyl]-2H-benzotriazole, 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'ethyloxanilide, 2,6-bis(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl-s-triazine, 2,6-bis(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine, 2,6-bis(2,4-dimethylphenyl)-[2-hydroxy -4-(2-hydroxy-3-dodecyloxypropanoxy)phenyl]-s-triazine and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

Additional compositions of interest include those which additionally contain an effective stabilizing amount of a phenolic antioxidant; those which additionally contain a hindered amine derivative; or which additionally contain a phosphite or phosphonite stabilizer.

Compositions of special interest also include those wherein the organic material is an enamel of high solids content used for an industrial finish; is used as a coil coating; is used as a penetrating wood finish or is used as a film-forming wood finish.

When the instant compounds also contain a reactive functional group, said compounds can be chemically bonded by either condensation or free radical addition reaction to the polymer substrate. This provides for a non-migrating, non-sublimable UV absorber stabilizer. Such reactive functional groups include hydroxy, amino, amido, carboxyl and ethylenically unsaturated moieties.

The various organic materials useful in the instant invention are described in detail later in this application as well as are the various coadditives whose concomitant use with the instant compounds is often found to be highly beneficial.

The resulting stabilized polymer compositions of the invention may optionally also contain from about 0.01 to about 5%, preferably from about 0.025 to about 2%, and especially from about 0.1 to about 1% by weight of various conventional additives, such as the materials listed below, or mixtures thereof.

1. Antioxidants

1.1. Alkylated monophenols, for example, 2,6-di-tert-butyl-4-methylphenol 2-tert-butyl-4,6-dimethylphenol 2,6-di-tert-butyl-4-ethylphenol 2,6-di-tert-butyl-4-n-butylphenol 2,6-di-tert-butyl-4-i-butylphenol 2,6-di-cyclopentyl-4-methylphenol 2-(α-methylcyclohexyl)-4,6-dimethylphenol 2,6-di-octadecyl-4-methylphenol 2,4,6-tri-cyclohexylphenol 2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones, for example, 2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butyl-hydroquinone 2,5-di-tert-amyl-hydroquinone 2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers, for example, 2,2'-thio-bis-(6-tert-butyl-4-methylphenol) 2,2'-thio-bis-(4-octylphenol) 4,4'-thio-bis-(6-tert-butyl-3-methylphenol) 4,4'-thio-bis-(6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example, 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol) 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol) 2,2'-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol) 2,2'-methylene-bis-(6-nonyl-4-methylphenol) 2,2'-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]2,2'-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]2,2'-methylene-bis-(4,6-di-tert-butylphenol) 2,2'-ethylidene-bis-(4,6-di-tert-butylphenol) 2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol) 4,4'-methylene-bis-(2,6-di-tert-butylphenol) 4,4'-methylene-bis-(6-tert-butyl-2-methylphenol ) 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane ethyleneglycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate]di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, calcium-salt

1.6. Acylaminophenols, for example, 4-hydroxy-lauric acid anilide 4-hydroxy-stearic acid anilide 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

1.7. Esters of β3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols, for example,

______________________________________methanol      diethylene glycoloctadecanol   triethylene glycol1,6-hexanediol         pentaerythritolneopentyl glycol         tris-hydroxyethyl isocyanuratethiodiethylene glycol         di-hydroxyethyl oxalic acid diamide______________________________________

1.8. Esters of β3-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols, for example,

______________________________________methanol      diethylene glycoloctadecanol   triethylene glycol1,6-hexanediol         pentaerythritolneopentyl glycol         tris-hydroxyethyl isocyanuratethiodiethylene glycol         di-hydroxyethyl oxalic acid diamide______________________________________

1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid for example, N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

2. UV absorbers and light stabilizers

2.1.2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-, 3',5'-di-tert-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-, 3-sec-butyl-5'-tert-butyl-, 4'-octoxy, 3',5'-di-tert-amyl-, 3',5'-bis-(α,α-dimethylbenzyl), 3'-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-, 3'-itodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-, and dodecylated-5'-methyl derivatives.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy-and 2'-hydroxy-4,4'-di -methoxy derivatives.

2.3. Esters of optionally substituted benzoic acids for example, phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.

2.4. Acrylates, for example, α-cyano-ββ-diphenylacrylic acid ethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5. Nickel compounds, for example, nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetra-methylbutyl)-phenol], such as the 1:1 or '1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyl-dithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.

2.6. Sterically hindered amines, for example bis-(2,2,6,6-tetramethylpiperidyl) sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid his-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-s-triazine, tris-(2,2,6,6-tetramethylpiperidyl)-nitrilo-triacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone ).

2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl -oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N '-bis (3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example 2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine; 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide, N-salicylal--N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine, N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine, 3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic acid dihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, di-isodecylpentaerythritol diphosphite, di-(2,4-di-tert-butylphenyl )penta-erythritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl) 4,4'-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl--N-octadecylhydroxylamine, N-heptadecyl--N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone, N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

8. Polyamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.

9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipic acid, diphenylacetic acid.

11. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, anti-static agents, blowing agents and thiosynergists such as dilauryl thiodipropionate or distearyl thiodipropionate.

The phenolic antioxidant of particular interest is selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocynurate, 1,1,3 ,-tris(2-methyl-4-hydroxy-5-tert-butyl-phenyl)butane, 1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)-hydrazide, and N,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

A most preferred phenolic antioxidant is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis-(4,6-di-tert-butylphenol).

The hindered amine compound of particular interest is selected from the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione, tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, 1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza -21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethyl-piperidine), polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetra-methyl-4-hydroxypiperidine and succinic acid, polycondensation product of 4,4'-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine ) and 1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine ),N,N',N",N" -tetrakis[(4,6-bis(butyl-2,2,6,6 -tetramethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diaza decane, mixed [2,2,6,6-tetramethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro [5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8, 10-tetraoxa-spiro[5.5]undecane)diethyl]1,2,3,4-butanetetracarboxylate, octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate), 4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one), N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide, N-1-acetyl-2,2,6,6,tetramethylpiperidin-4-yln-dodecylsuccinimide, 1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-[[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino], and 2,4,6-Iris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

A most preferred hindered amine compound is bis(2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octyl-amino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,N',N",N"'-tetrakis[(4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)-s-triazine-2-yl]-1, 10-diamino-4,7-diazadecane. di-(1-octyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino], or 2,4,6-Iris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

The following examples are for illustrative purposes only and are not to be construed to limit the scope of the instant invention in any manner whatsoever.

EXAMPLE 1 2-(2,4-Dihydroxy-5-hexylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 500 mL three-necked, round-bottomed flask equipped with a magnetic stirrer, condenser, and a nitrogen atmosphere are charged 5.10 g (16.0 mmol) of 2-chloro-4,6-bis-(2,4-dimethylphenyl)-s -triazine, 3.10 g (16.0 mmol) of hexylresorcinol, and 40 mL of tetrachloroethane. The mixture becomes homogeneous with gentle warming after which 2.10 g (16.0 mmol) of aluminum chloride are added quickly in small portions. The mixture is heated for five hours with an oil bath maintained at 148° C., and is allowed to sit overnight at room temperature. Following the addition of 200 mL of 2 N hydrochloric acid, the mixture is refluxed for two hours. After cooling to room temperature, a portion of ethyl acetate is added and the layers are separated. The aqueous layer is extracted twice more with ethyl acetate and the combined organic layers are dried over anhydrous magnesium sulfate. Following filtration, the solvent is removed under reduced pressure to afford 7.35 g of yellow solid. The crude product is recrystallized from ethyl acetate/heptane to yield 4.15 g of the title compound as a yellow solid; mp 165°-167° C.

1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 288; 348 nm (ε38,000; 16,200).

Analysis: Calcd for C31 H35 N3 O2 : C, 77.3; H, 7.3; N, 8.7. Found: C, 77.2; H, 7.3; N, 8.7.

EXAMPLE 2 4,6-Bis-(2,4-dimethylphenyl)-2-[5-hexyl-2-hydroxy-4-(2-hydroxy-3-phenoxypropoxy)-phenyl ]-s-triazine

To a 500 mL round-bottomed flask equipped with a magnetic stirrer, condenser, and a nitrogen atmosphere are charged 3.88 g (8.10 mmol) of the product of Example 1, 30 mL of 1,2-epoxy-3-phenoxypropane, and 200 mg of triphenylethylphosphonium iodide. The mixture is stirred at an external temperature of 210° C. for six hours. After cooling to room temperature, excess epoxide is removed under reduced pressure and the residue is dissolved in a portion of 3:1 heptane:ethyl acetate. The solution is passed through a plug of silica gel and the solvent is removed to yield 7.70 g of orange solid. The crude product is purified with medium pressure chromatography with 3:1 heptane:ethyl acetate followed by recrystallization from heptane to afford 1.17 g of the title compound as a yellow solid; mp 110°-111° C.

1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 288; 350 nm (ε40,500; 19,500).

Analysis: Calcd for C40 H45 N3 O4 : C, 76.0; H, 7.2; N, 6.7. Found: C, 75.7; H, 7.4; N, 6.5.

EXAMPLE 3

4,6-Bis-(2,4-dimethylphenyl)-2-[4-(3-dodecyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-s-triazine

To a 1 L three-necked, round-bottomed flask equipped with a magnetic stirrer, condenser, thermometer, and a nitrogen atmosphere are charged 15.0 g (31.1 mmol) of the product of Example 1, 12.0 g (46.9 mmol) of glycidyl dodecyl* ether, and 770 mg of triphenylethylphosphonium iodide. The mixture is stirred at 210° C. for eight hours. After cooling to room temperature, excess epoxide is removed under reduced pressure. The crude product is taken up in ethyl acetate, passed through a plug of silica gel and purified with medium pressure chromatography with 3:1 heptane:ethyl acetate to afford 16.4 g of the title compound as an orange glassy solid.

1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 290; 350 nm (ε49,500 and 23,900).

EXAMPLE 4 2-(2,4-Dihydroxy-5-ethylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 500 mL round-bottomed flask equipped with a magnetic stirrer, condenser, and a nitrogen atmosphere are charged 5.14 g (15.9 mmol) of 2-chloro-4,6-bis-(2,4-dimethylphenyl) -s-triazine, 2.20 g (15.9 mmol) of 4-ethylresorcinol, and 40 mL of tetrachloroethane. After gentle warming to dissolve the mixture, 2.13 g (15.9 mmol) of aluminum chloride are added quickly in small portions. The mixture is stirred and heated at an external temperature of 145° C. for 5.5 hours. After sitting overnight at room temperature, 200 mL of 2 N hydrochloric acid are added and the mixture is refluxed for three hours. After cooling to room temperature, a portion of ethyl acetate is added and the layers are separated. The aqueous layer is extracted twice more with ethyl acetate and the combined organic layers are washed once with brine and are dried over anhydrous magnesium sulfate. Following filtration, the solvent is removed under reduced pressure to yield 7.10 g of a yellow solid. The crude solid is recrystallized from 3:1 heptane:ethyl acetate to afford 2.21 g of the title compound as a yellow solid; mp 193°-195° C.

1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 288; 348 nm (ε40,400; 18,300).

Analysis: Calcd for C27 H27 N3 O2 : C, 76.2; H, 6.4; N, 9.9. Found: C, 76.2; H, 6.4; N, 10.1.

EXAMPLE 5 2-[2,4-Dihydroxy-5-(1,1-dimethylethyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 250 mL round-bottomed flask equipped with a magnetic stirrer, condenser, and a nitrogen atmosphere are charged 440 mg (1.11 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine, 2 mL of diisobutylene, and 6 mL of methanesulfonic acid. The mixture is stirred at an external temperature of 75° C. for three hours. The mixture is allowed to cool to room temperature, and equal portions of ethyl acetate and water are added. The layers are separated and the organic layer is washed once with water, twice with saturated sodium bicarbonate solution, once with brine and is dried over anhydrous magnesium sulfate. Following filtration, the solvent is removed under reduced pressure to yield 1.28 g of yellow solid. The crude solid is purified with medium pressure chromatography with 3:1 heptane:ethyl acetate to afford 59 mg of the title compound as a yellow solid.

1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 290; 346 nm (ε29,400; 16,600).

EXAMPLE 6 2-[2,4-Dihydroxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 1 L three-necked, round-bottomed flask equipped with a magnetic stirrer, condenser, dropping funnel, thermometer, and a nitrogen atmosphere are charged 15.0 g (37.8 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 390 mg of aluminum isopropoxide. The mixture is heated to 175° C. and 4.47 g (37.9 mmol) of α-methylstyrene are added dropwise at a rate of one drop every two seconds. A total of six equivalents of a-methyl styrene are added in this fashion over a 4.5 hour period. After cooling to room temperature, the mixture is diluted with ethyl acetate, washed twice with water and once with brine, and is dried over anhydrous magnesium sulfate. Following filtration, the solvent is removed under reduced pressure to yield a yellow solid. The crude product is purified with medium pressure chromatography with 12% ethyl acetate/heptane to afford 13.2 g of the title compound as a yellow solid; mp 168°-170° C.

1 nmr (CDCl3) spectrum is consistent with the desired product; UV λmax (ethyl acetate) 290; 347 nm (ε45,700; 23,300).

EXAMPLE 7 4,6-Bis-(2,4-dimethylphenyl)-2-[2-hydroxy-4-(2-hydroxy-3-nonyloxypropoxy)-5-(1-methyl-1-phenylethyl)phenyl]-s-triazine

Following the general procedure of Example 3, 4.59 g (8.91 mmol) of the product of Example 6, 3.10 g (16.9 mmol) of glycidyl nonyl* ether, and 510 mg of triphenylethyl-phosphonium iodide are reacted at 160° C. for seven hours. The product is worked up as in Example 3 to afford 3.82 g of title compound as a waxy clear brown solid.

1 H nmr (CDCl3) and mass spectra are consistent with the desired product; UV λmax (ethyl acetate) 291; 348 nm (ε36,600; 19,000).

EXAMPLE 8 4,6-Bis-(2,4-dimethylphenyl)-2-[4-hexyloxy-2-hydroxy-5-(1-methyl-1-phenylethyl)-phenyl ]-s-triazine

To a 500 mL three-necked, round-bottomed flask equipped with a magnetic stirrer, condenser, thermometer, and a nitrogen atmosphere are charged 5.50 g (10.7 mmol) of the product of Example 6 and 50 mL of N,N-dimethylformamide. After warming to form a homogeneous solution, 0.43 g (17.9 mmol) of sodium hydride and 2.26 g (10.7 mmol) of 1-iodohexane are added. The mixture is stirred at 40° C. for four hours. After cooling to room temperature, the mixture is poured into a beaker of water. Vacuum filtration affords 4.64 g of the title compound as a yellow solid; mp 111°-115° C.

1 H nmr (CDCl3) and mass spectra are consistent with the desired product; UV λmax (ethyl acetate) 290; 348 nm (ε41,700; 22,300).

EXAMPLE 9 2-[2,4-Dihydroxy-5-(1-methyl-1-phenylethyl)phenyl]-4,6-bis-phenyl-s-triazin

To a 500 mL three-necked, round-bottomed flask equipped with a magnetic stirrer, dropping funnel, condenser, thermometer, and a nitrogen atmosphere are charged 5.00 g (14.7 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-phenyl-s-triazine and 300 mg of aluminum isopropoxide. The mixture is heated to 160° C. and 17.3 g of α-methylstyrene are added all at once. After stirring at this temperature for 26 hours the mixture is allowed to cool and a portion of heptane is added. Vacuum filtration affords 4.45 g of the title compound as a yellow solid.

1 H nmr (CDCl3) and mass spectra are consistent with the desired product.

EXAMPLE 10 2-[2-Hydroxy-5-(1-methyl-1-phenylethyl)-4-octyloxyphenyl]-4,6-bis-phenyl-s-triazine

To a 500 mL three-necked, round-bottomed flask equipped with a condenser, magnetic stirrer, thermometer, and a nitrogen atmosphere are charged 4.00 g (8.71 mmol) of the product of Example 9, 50 mL of N,N-dimethylformamide and 0.40 g (10 mmol) of sodium hydride (60 % in mineral oil). The mixture is heated to an external temperature of 50° C. and 1.68 g (8.70 mmol) of 1-bromooctane are added. The mixture is stirred at this temperature for six hours and is allowed to cool to room temperature. The mixture is poured into a beaker of water which is extracted four times with chloroform. The combined chloroform layers are washed four times with water and dried over anhydrous magnesium sulfate and filtered. The solvent is removed under reduced pressure to afford a yellow oil. The crude product is purified with medium pressure chromatography with 10:1 heptane:ethyl acetate followed by recrystallization from acetone/water to yield 1.12 g of the title compound as a yellow solid.

1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 271; 351 nm (ε44,000; 24,000).

EXAMPLE 11 2-(5--Chloro-2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 1 L three-necked, round-bottomed flask equipped with a magnetic stirrer, thermometer, condenser, and a nitrogen atmosphere are charged 20.0 g (61.9 mmol) of 2-chloro-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 50 mL of tetrachloroethane. The mixture is warmed to dissolve the solids and 8.24 g (62.0 mmol) of aluminum chloride are added in small portions all at once followed by 9.00 g (62.1 mmol) of 4-chlororesorcinol. The mixture is stirred at 120° C. for four hours. After cooling to room temperature 50 mL of water and 10 mL of concentrated hydrochloric acid are added and the mixture is refluxed for two hours. After cooling, the mixture is extracted thrice with ethyl acetate and the combined organic layers are dried over anhydrous magnesium sulfate and filtered. The solvent is removed under reduced pressure to yield a yellow solid. Recrystallization from ethyl acetate/heptane affords 8.65 g of the title compound as a yellow solid.

1 nmr (CDCl3) and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 248; 345 nm (ε48,000; 19,000).

EXAMPLE 12 2-(2,4-Dihydroxy-5-propionylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 500 mL three-necked, round-bottomed flask equipped with a mechanical stirrer, condenser, and a nitrogen atmosphere are charged 5.33 g (13.0 mmol) of 2-(2,4-di-hydroxyphenyl)-4,6-bis -(2,4-dimethylphenyl)-s-triazine and 20 mL of tetrachloroethane. The mixture is warmed to an external temperature of 40° C. and 4.33 g (32.5 mmol) of aluminum chloride are added quickly in small portions. A solution of 1.20 g (13.0 mmol) of propionyl chloride in 20 mL tetrachloroethane is added dropwise over 15 minutes. The mixture is stirred at an external temperature of 110° C. for four hours. After cooling to room temperature, 50 mL of water and 6 mL of concentrated hydrochloric acid are added and the mixture is stirred with warming for two hours. A portion of ethyl acetate is added with warming to dissolve all of the solids. The layers are separated and the aqueous layer is extracted once more with ethyl acetate. The combined organic layers are dried over anhydrous magnesium sulfate and filtered. The product is allowed to crystallize and 2.14 g of the title compound is collected by vacuum filtration as a yellow solid.

1 H nmr (CDCl3), infrared and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 270; 338 nm (ε49,500; 17,500).

EXAMPLE 13 2-[2,4-Dihydroxy-5-(1-isobutylimino)propylphenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine

The product of Example 12 (410 mg, 0.900 mmol) is dissolved in isobutylamine with warming. The solution is allowed to stand for one hour. A portion of water is added, the mixture is vacuum filtered and the precipitate is washed with ethyl acetate. The solid is air dried to yield 300 mg of the title compound as a yellow solid.

1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 276; 348 nm (ε28,700; 16,100).

EXAMPLE 14 2-[2,4-Dihydroxy-5-(1-isobutylamino)propylphenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 100 mL round-bottomed flask equipped with a magnetic stirrer are charged 67 mg (0.13 mmol) of the product of Example 13, 4 mL of acetic acid, and 50 mg of sodium borohydride. The mixture is stirred for one hour. Portions of ethyl acetate and water are added and the layers are separated. The organic layer is washed twice with water, twice with saturated sodium bicarbonate solution, once with brine, and is dried over anhydrous magnesium sulfate. Following filtration, the solvent is removed under reduced pressure to yield 73 mg of the title compound as a clear yellow oil.

1 H nmr (CDCl3), infrared and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 288; 348 nm (ε28,900; 17,500).

EXAMPLES 15-18

Following the general procedure of Example 1, 4 or 11, the substituted s-triazine compounds indicated below are prepared.

______________________________________Ex         2-(2,4-dihydroxy-5-)                        4,6-di-______________________________________15         methyl            xylyl16         methyl            phenyl17         ethyl             phenyl18         chloro            xylyl______________________________________
EXAMPLE 19 2-(2,4-Dihydroxy-5-hexylphenyl)-4,6-diphenyl-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser and a nitrogen atmosphere are charged 21.4 g (80 mmol) of 2-chloro-4,6-diphenyl-s-triazine, and 100 mL of xylene (mixture of isomers). To the beige suspension are added 11.3 g (85 mmol) of aluminum chloride in one portion. The mixture is warmed to ca. 80° C. for 45 minutes. 18.8 g (96 mmol) of 4-hexylresorcinol are then added in five portions over 40 minutes to the now homogeneous solution. The reaction mixture is heated at 90° C. for 24 hours. After cooling to room temperature, the contents of the flask are poured into 100 mL of 12% aqueous hydrochloric acid. The precipitate formed is removed by filtration, washed to pH 7 with water, rinsed with methanol and dried at 70° C. under vacuum. The title compound is obtained as a crude orange product (29.2 g) and melts at 209°-213° C. It can be used without further purification.

EXAMPLES 20-24

Following the general procedure of Example 5, 6 or 9, the substituted s-triazine compounds indicated below are prepared.

______________________________________Ex         2-(2,4-dihydroxy-5-)                        4,6-di-______________________________________20         tert-butyl        phenyl21         dodecyl           phenyl22         dodecyl           xylyl23         octyl             xylyl24         octyl             phenyl______________________________________
EXAMPLES 25-33

Following the general procedure of Example 2, 3 or 7, the substituted s-triazine compounds indicated below are prepared.

______________________________________Ex     2-(2-hydroxy-)           4,6-di-______________________________________25     5-hexyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.9 H.sub.19                           xylyl26     5-α-cumyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.5                           xylyl27     5-α-cumyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.5                           phenyl28     5-α-cumyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.12 H.sub.25                           xylyl29     5-hexyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.6 H.sub.5                           phenyl30     5-hexyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.9 H.sub.19                           phenyl31     5-hexyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.12 H.sub.25                           phenyl32     5-α-cumyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.12 H.sub.25                           phenyl33     5-α-cumyl-4-OCH.sub.2 CHOHCH.sub.2 OC.sub.9 H.sub.19                           phenyl______________________________________
EXAMPLE 34 4,6-Diphenyl-2-(5-hexyl-4-hexyloxy-2-hydroxyphenyl)-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser, dropping funnel and a nitrogen atmosphere are charged 20.0 g (47 mmol) of the product of Example 19, 6.5 g (47 mmol) of potassium carbonate, 50 mg of potassium iodide, and 50 mL of 2-ethoxyethanol. The suspension is warmed to 110° C., and 8.5 g (51 mmol) of 1-bromohexane are added dropwise over 30 minutes. After 22 hours, the reaction mixture is cooled to room temperature, the precipitate is removed by filtration, washed with water to pH 6, rinsed with methanol and dried at 70° C. under vacuum. The crude yellow product (19 g) is recrystallized twice from 100 mL of 2-ethoxyethanol to give the title compound in a yield of 15.6 mg as a yellow solid melting at 140°-141° C., purity 98.8% (DSC assay).

1 H nmr (CDCl3) spectrum is consistent with the desired product; UV λmax (chloroform) 273; 355 nm (ε42,000; 20,000)

Analysis: Calcd for C33 H39 N3 O2 : C, 77.8; H, 7.7; N, 8.2. Found: C, 77.6; H, 7.9; N, 8.2.

EXAMPLE 35 4,6-B is (2,4-dimethylphenyl)-2-(5-hexyl-4-hexyloxy-2-hydroxyphenyl)-s-triazine

To a 200 mL sulfonation flask equipped with a mechanical stirrer, condenser, dropping funnel and a nitrogen atmosphere are charged 14.5 g (30 mmol) of the product of Example 1, 4.6 g (33 mmol) of potassium carbonate, 50 mg of potassium iodide, and 60 mL of 2-ethoxyethanol. The suspension is warmed to 110° C., and 5.5 g (33 mmol) of 1-bromohexane are added dropwise over 20 minutes. After 16 hours, another portion of 1-bromohexane (5.5 g, 33 mmol) is added and heating is continued for another eight hours. The reaction mixture is cooled to room temperature, the precipitate is removed by filtration, washed with water to pH 6, rinsed with methanol and dried at 70° C. under vacuum. The crude yellow product (13.9 g) is recrystallized twice from 300 mL of 2-ethoxyethanol to give the title compound in a yield of 10.7 g as a yellow solid melting at 78°-80° C., purity 99.1% (DSC assay).

1 H nmr (CDCl3) spectrum is consistent with the desired product; UV λmax (chloroform) 293; 353 nm (ε42,000; 21,000)

Analysis: Calcd for C37 H47 N3 O2 : C, 78.5; H, 8.4; N, 7.4. Found: C, 78.0; H, 8.3; N, 7.4.

EXAMPLES 36-45

Following the general procedure of Example 8 or 10, the substituted s-triazine compounds indicated below are prepared.

______________________________________Ex        2-(2-hydroxy-)      4,6-di-______________________________________36        5-hexyl-4-dodecyloxy                         xylyl37        5-hexyl-4-dodecyloxy                         phenyl38        5-hexyl-4-octyloxy  xylyl39        5-hexyl-4-octadecyloxy                         phenyl40        5-hexyl-4-octadecyloxy                         xylyl41        5-α-cumyl-4-dodecyloxy                         phenyl42        5-α-cumyl-4-dodecyloxy                         xylyl43        5-α-cumyl-4-octyloxy                         xylyl44        5-α-cumyl-4-octadecyloxy                         phenyl45        5-α-cumyl-4-octadecyloxy                         xylyl______________________________________
EXAMPLE 46 4,6-Bis-(2,4-dimethylphenyl)-2-[2,4-dihydroxy-5-(1-hydroxypropyl)phenyl]-s-triazine

To a 500 mL 3-necked, round-bottomed flask equipped with a condenser, magnetic stirrer, thermometer, dropping funnel, and a nitrogen atmosphere are charged 25 mL of tetrahydrofuran and 0.89 g (24 mmol) of lithium aluminum hydride. A solution of 2.00 g (4.42 mmol) of the product of Example 12 in 250 mL of tetrahydrofuran is added dropwise over 30 minutes to the stirred suspension. The mixture is stirred at room temperature for 3.5 hours and the excess lithium aluminum hydride is quenched with portions of ethyl acetate followed by water. Anhydrous magnesium sulfate is added, the mixture is filtered, and the solvent is removed under reduced pressure. The crude product is purified with flash chromatography with 3:1 heptane:ethyl acetate to afford 0.27 g of the title compound as a yellow solid.

1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 289; 344 nm (ε45,000; 18,700).

EXAMPLE 47 2-(5-Benzoyl-2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 500 mL three-necked, round-bottomed flask equipped with a mechanical stirrer, condenser, dropping funnel, and a nitrogen atmosphere are charged 5.57 g (14.0 mmol) of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine and 25 mL of tetrachloroethane. The mixture is warmed to an external temperature of 90° C. and 2.88 g (20.5 mmol) of benzoyl chloride in 20 mL of tetrachloroethane are added dropwise over 45 minutes. The mixture is stirred at an external temperature of 145° C. for six hours and is allowed to sit at room temperature overnight. Fifty mL of water and 5 mL of concentrated hydrochloric acid are added and the mixture is stirred with warming for three hours. A portion of ethyl acetate is added and the mixture is warmed to dissolve any organic solids. The layers are separated, the aqueous layer is washed with ethyl acetate and the combined organic layers are dried over anhydrous magnesium sulfate and filtered. The product is allowed to crystallize from solution and 3.55 g of the title compound (off-white needles) are collected by vacuum filtration.

1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 282; 340 nm (ε61,400; 15,600).

EXAMPLE 48 4,6-Bis-(2,4-dimethylphenyl)-2-[2,4-dihydroxy-5-(α-hydroxybenzyl)phenyl]-s-triazine

To a 300 mL 3-necked, round-bottomed flask equipped with a dropping funnel, condenser, magnetic stirrer, and a nitrogen atmosphere are charged 20 mL of tetrahydrofuran and 0.26 g (6.8 mmol) of lithium aluminum hydride. A solution of 0.50 g (1.0 mmol) of the product of Example 47 in 30 mL of tetrahydrofuran is added over ten minutes to the stirred suspension. The mixture is refluxed for two hours and is allowed to cool to room temperature. Excess lithium aluminum hydride is quenched with portions of ethyl acetate followed by water. Anhydrous magnesium sulfate is added, the mixture is filtered, and the solvent is removed under vacuum to afford 0.35 g of the title compound as a yellow solid.

1 H nmr (CDCl3) and mass spectra are consistent with the title compound; UV λmax (ethyl acetate) 288; 343 nm (ε32,400; 13,500).

EXAMPLE 49 2-(2,4-Dihydroxy-5-phenylthiophenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazin

To a 500 mL 3-necked, round-bottomed flask equipped with a magnetic stirrer, condenser, thermometer, and a nitrogen atmosphere are charged 1.30 g (3.0 mmol) of the product of Example 11, 5 mL of N-methylpyrrolidinone, and 0.51 g (9.1 mmol) of potassium hydroxide. The mixture is stirred and heated to 140° C. and 0.33 g (3.0 mmol) of thiophenol is added all at once. After 15 hours the mixture is allowed to cool to room temperature. A portion of 10% aqueous hydrochloric acid is added with stirring. The mixture is filtered and the solids are washed with water followed by heptane. The crude product is recrystallized from ethyl acetate to afford 0.56 g of the title compound as an off-white solid.

1 H nmr (CDCl3) and mass spectra are consistent with the desired compound; UV λmax (ethylacetate) 289; 339 nm (ε51,000; 18,000).

EXAMPLE 50 2-(2,4-Dihydroxy-5-phenylsulfinylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 250 mL 3-necked, round-bottomed flask equipped with a condenser, magnetic stirrer, thermometer, and a nitrogen atmosphere are charged 0.25 g (0.49 mmol) of the product of Example 49, 0.059 g (0.98 mmol) of acetic acid, and 20 mL of 2-propanol. The mixture is heated to reflux and 0.067 g (1.0 mmol) of 50% hydrogen peroxide are added. The mixture is refluxed for one hour and is allowed to cool to room temperature. A portion of ethyl acetate is added and the organic layer is washed twice with 10% aqueous sodium metabisulfite, twice with saturated sodium bicarbonate, once with brine, and is dried over anhydrous magnesium sulfate. After filtering, the solvent is removed under reduced pressure to yield a yellow solid. Purification by flash chromatography with 3:1 heptane:ethyl acetate yields 0.11 g of the title compound as a yellow solid.

1 H nmr (1,1,2,2-tetrachloroethane-d2) spectrum is consistent with the desired compound; UV λmax (tetrahydrofuran) 279; 373 nm (ε23,000; 23,000).

EXAMPLE 51 2-(2,4-Dihydroxy-5-phenylsulfonylphenyl)-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 250 mL 3-necked, round-bottomed flask equipped with a magnetic stirrer, condenser, thermometer, and a nitrogen atmosphere are charged 0.27 g (0.54 mmol) of the compound of Example 50, 0.80 g (1.3 mmol) of acetic acid, 0.10 g (1.0 mmol) of sulfuric acid, and 20 mL of 2-propanol. The mixture is heated to reflux and 0.077 g (1.1 mmol) of 50% hydrogen peroxide are added. After five hours, the mixture is allowed to cool to room temperature and a portion of ethyl acetate is added. The organic layer is washed twice with 10% aqueous sodium metabisulfite, twice with saturated sodium bicarbonate, once with brine, and is dried over anhydrous magnesium sulfate. After filtering, the solvent is removed under reduced pressure to afford a yellow solid. Purification with flash chromatography with 1:3 heptane:ethyl acetate affords 0.11 g of the title compound as a yellow solid.

1 H nmr (tetrahydrofuran-d8) and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 276; 377 nm (ε30,000; 31,000).

EXAMPLES 52-53

Using the general procedures of Examples 5, 6 and 9, the following compounds of formula IV are prepared.

______________________________________Ex     X, X, Y, Y'             R.sub.2 and R.sub.2 '                        L______________________________________52     xylyl      hydrogen   1-(2,2-isopropyli-                        dene)-4-methyl-1,4-                        cyclohexylene53     xylyl      hydrogen   α,α,α',α'-tetramethyl                        -                        m-xylylene______________________________________
EXAMPLE 54 2-(5--Chloro-2,4-dihydroxyphenyl)-4,6-diphen yl-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser and a nitrogen atmosphere are charged 26.8 g (100 mmol) of 2-chloro-4,6-diphenyl-s-triazine, and 100 mL of xylene (mixture of isomers). To the beige suspension are added 14.9 g (112 mmol) of aluminum chloride in one portion. The mixture is warmed to ca. 80° C. for 2 hours. 17.4 g (120 mmol) of 4-chlororesorcinol are then added in five portions over 40 minutes to the now homogeneous solution. The reaction mixture is heated at 90° C. for 42 hours and refluxed for another 24 hours. After cooling to room temperature, the contents of the flask are poured into 100 mL of 12% aqueous hydrochloric acid. The precipitate formed is removed by filtration, washed to pH 7 with water, rinsed with methanol and dried at 70° C. under vacuum. The title compound is obtained as a crude ocher-red product (29.5 g) and melts at 255°-265° C. It can be used without further purification.

EXAMPLE 55 4,6-Diphenyl-2-(5-chloro-4-hexyloxy-2-hydroxyphenyl)-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser, dropping funnel and a nitrogen atmosphere are charged 26.3 g (70 mmol) of the product of Example 54, 10.6 g (77 mmol) of potassium carbonate, 50 mg of potassium iodide, and 50 mL of 2-ethoxyethanol. The suspension is warmed to 110° C., and 10.8 g (77 mmol) of 1-bromohexane are added dropwise over 30 minutes. After 8 hours, the reaction mixture is cooled to room temperature, the precipitate is removed by filtration, washed with water to pH 6, rinsed with methanol and dried at 70° C. under vacuum. The crude beige product (26.9 g) is recrystallized twice from 600 mL of 2-ethoxyethanol to give the title compound in a yield of 18.6 g as a yellow solid melting at 147°-149° C., purity 98.7% (DSC assay).

1 H nmr (CDCl3) spectrum is consistent with the desired product; UV λmax (chloroform) 281; 351 nm (ε45,000; 18,400)

EXAMPLE 56 4,6-Diphenyl-2-(5-hexyl-4-methoxy-2-hydroxyphenyl)-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser, dropping funnel and a nitrogen atmosphere are charged 20.0 g (47 mmol) of the product of Example 19, 7.2 g (52 mmol) of potassium carbonate and 100 mL of 2-ethoxyethanol. The suspension is warmed to 50° C., and 13.3 g (94 mmol) of methyl iodide are added dropwise over 45 minutes. After 14 hours, the reaction mixture is cooled to room temperature, the precipitate is removed by filtration, washed with water to pH 6, rinsed with methanol and dried at 70° C. under vacuum. The crude yellow product (16.1 g) is recrystallized thrice from 2-ethoxyethanol to give the title compound in a yield of 9.8 g as a yellow solid melting at 186°-188° C., purity 94.1% (DSC assay).

1 H nmr (CDCl3) spectrum is consistent with the desired product; UV λmax (chloroform) 275; 354 nm (ε41,900; 18,500)

Analysis: Calcd for C28 H29 N3 O2 : C, 76.5; H, 6.7; N, 9.6. Found: C, 75.3; H, 6.8; N, 9.4.

EXAMPLE 57 2-[4-(3-Butyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-4,6-diphenyl-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser, and a nitrogen atmosphere are charged 8.5 g (20 mmol) of the product of Example 19, 0.4 g (1 mmol) of triphenylethylphosphonium bromide, 3.0 g (22 mmol) of butyl glycidyl ether and 50 mL of xylene (mixture of isomers). The thick orange suspension is refluxed for 24 hours. The reaction mixture is then cooled to room temperature, the precipitate is removed by filtration, washed with a small amount of xylene, rinsed with methanol and dried at 70° C. under vacuum. The crude yellow product (9.0 g) is recrystallized twice from 20 mL of 2-ethoxyethanol to give the title compound in a yield of 6.0 g as a yellow solid melting at 145°-146° C., purity 98.2% (DSC assay).

1 H nmr (CDCl3) spectrum is consistent with the desired product; UV λmax (chloroform) 275; 354 nm (ε43,000; 19,000)

Analysis: Calcd for C34 H41 N3 O4 : C, 73.5; H, 7.4; N, 7.6. Found: C, 73.6; H, 7.5; N, 7.5.

EXAMPLE 58 2-(2,4-Dihydroxy-5-hexylphenyl)-4,6-bis(4-methylphenyl)-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser and a nitrogen atmosphere are charged 29.6 g (100 mmol) of 2-chloro-4,6-bis(4-methylphenyl)-s-triazine, and 100 mL of xylene (mixture of isomers). To the beige suspension are added 11.3 g (85 mmol) of aluminum chloride in one portion. The mixture is warmed to ca. 90° C. for 75 minutes. 21.4 g (110 mmol) of 4-hexylresorcinol are then added in five portions over 45 minutes to the now homogeneous solution. The reaction mixture is heated at 90° C. for 18 hours. After cooling to room temperature, the contents of the flask are poured into 120 mL of 6% aqueous hydrochloric acid. The precipitate formed is removed by filtration, washed to pH 7 with water, rinsed with methanol and dried at 70° C. under vacuum. The title compound is obtained as a crude orange product (43.1 g) and melts at 228°-231° C. It can be used without further purification.

EXAMPLE 59 4,6-Bis(4-methylphenyl)-2-(5-hexyl-4-hexyloxy-2-hydroxyphenyl)-s-triazine

To a 200 mL sulfonation flask equipped with a mechanical stirrer, condenser, dropping funnel and a nitrogen atmosphere are charged 13.6 g (30 mmol) of the product of Example 58, 4.6 g (33 mmol) of potassium carbonate, 50 mg of potassium iodide, and 70 mL of 2-ethoxyethanol. The suspension is warmed to 110° C., and 5.5 g (33 mmol) of 1-bromohexane are added dropwise over 30 minutes. After 20 hours, another portion of 1-bromohexane (5.5 g, 33 mmol) is added and heating is continued for another 25 hours. The reaction mixture is cooled to room temperature, the precipitate is removed by filtration, washed with water to pH 6, rinsed with methanol and dried at 70° C. under vacuum. The crude yellow product (13.6 g) is recrystallized from 350 mL of 2-ethoxyethanol to give the title compound in a yield of 10.6 g as a yellow solid melting at 137°-138° C., purity 96.9% (DSC assay).

1 H nmr (CDCl3) spectrum is consistent with the desired product; UV λmax (chloroform) 293; 354 nm (ε56,000; 21,500)

Analysis: Calcd for C35 H43 N3 O2 : C, 78.2; H, 8.1; N, 7.8. Found: C, 77.5; H, 8.2; N, 7.8.

EXAMPLE 60 2-[4-(3-Butyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-4,6-bis(4-methylphenyl) -s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser, and a nitrogen atmosphere are charged 13.6 g (30 mmol) of the product of Example 58, 0.6 g (1.5 mmol) of triphenylethylphosphonium bromide, 4.5 g (33 mmol) of butyl glycidyl ether and 40 mL of xylene (mixture of isomers). The thick orange suspension is refluxed for 21 hours. The reaction mixture is then cooled to room temperature, the precipitate is removed by filtration, washed with water, rinsed with methanol and dried at 70° C. under vacuum. The crude yellow product (14 g) is recrystallized twice from 50 mL of 2-ethoxy-ethanol to give the title compound in a yield of 9.3 g as a yellow solid melting at 163°-164° C., purity 98.8% (DSC assay).

1 H nmr (CDCl3) spectrum is consistent with the desired product; UV λmax (chloroform) 293; 35 1 nm (ε59,000; 20,000)

Analysis: Calcd for C36 H45 N3 O4 : C, 74.1; H, 7.8; N, 7.2. Found: C, 73.4; H, 7.8; N, 7.1.

EXAMPLE 61 2-[4-(3-Butyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser, and a nitrogen atmosphere are charged 14.4 g (30 mmol) of the product of Example 1, 0.6 g (1.5 mmol) of triphenylethylphosphonium bromide, 4.5 g (33 mmol) of butyl glycidyl ether and 40 mL of xylene (mixture of isomers). The thick orange suspension is refluxed for 24 hours. The reaction mixture is then cooled to room temperature, the precipitate is removed by filtration, washed with water, rinsed with methanol and dried at 70° C. under vacuum. The filtrate is concentrated on a rotary evaporator to yield a second crop of crude product. The combined solids (14.9 g) are recrystallized from 45 mL of 2-ethoxyethanol to give the title compound in a yield of 9.0 g as a yellow solid melting at 101°-102° C., purity 97.3% (DSC assay).

1 H nmr (CDCl3) spectrum is consistent with the desired product; UV λmax (chloroform) 292; 350 nm (ε49,000; 21,000)

Analysis: Calcd for C38 H49 N3 O4 : C, 74.6; H, 8.1; N, 6.9. Found: C, 74.5; H, 8.0; N, 6.9.

EXAMPLE 62 2,4-Bis(2,4-dihydroxy-5-hexylphenyl)-6-phenyl-s-triazine

To a 750 mL sulfonation flask equipped with a mechanical stirrer, condenser, dropping funnel and a nitrogen atmosphere are charged 34.0 g (150 mmol) of 2,4-dichloro-6-phenyl-s-triazine, 44.0 g (330 mmol) of aluminum chloride and 100 mL of ligroin (boiling range 110°-140° C). To that suspension, 60 mL of sulfolane are added dropwise with stirring over a 15 minute period with the temperature rising to 50° C. A solution of 62.1 g (320 retool) of 4-hexylresorcinol in 60 mL of sulfolane is then added dropwise over a 15 minute period. The temperature rises to 60° C. and hydrogen chloride is evolved. The reaction mixture is heated to 80° C. for four hours. The lower layer of the two-phase mixture is poured into a solution of 50 mL of concentrated hydrochloric acid in 500 mL of methanol and 300 mL of water. The mixture is stirred at room temperature for 14 hours. The product obtained is suspended in 800 mL of water at 80° C. for 1 hour, is isolated by filtration and resuspended under the same conditions, finally isolated and dried at 85° C. under vacuum. The title compound is obtained as a crude orange product (77.0 g) and melts at 230°-238° C. It can be used without further purification.

1 H nmr (DMSO-d6) spectrum is consistent with the desired product.

Analysis: Calcd for C33 H39 N3 O4 : C, 73.2; H, 7.3; N, 7.8. Found: C, 73.2; H, 7.3; N, 7.6.

EXAMPLE 63 2,4Bis[4-(3-butyloxy-2-hydroxypropoxy)-5-hexyl-2-hydroxyphenyl]-6-phenyl-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser, and a nitrogen atmosphere are charged 16.2 g (30 mmol) of the product of Example 62, 1.1 g (3 mmol) of triphenylethylphosphonium bromide, 8.6 g (66 mmol) of butyl glycidyl ether and 120 mL of mesitylene. The thick orange suspension is heated at 130° C. for 18 hours to form a brown solution. The solvent is removed using a rotary evaporator. The crude product is dissolved in 100 mL of ethyl acetate. The solution is filtered through a pad of 230°-400 mesh silica (100 g, 10 cm diameter) using 1000 mL of ethyl acetate as eluent. After evaporation of the solvent, the yellow resin (25.9 g) is redissolved in 50 mL of ethyl acetate and precipitated with 150 mL of hexane to give 20 g of product. This material is recrystallized from 70 mL of ethyl acetate and dried at 75° C. under vacuum to give the 15.9 g of the title compound as a resinous orange solid melting at 108°-115° C.

1 H nmr (CDCl3) spectrum is consistent with the desired product; UV λmax (chloroform) 298; 369 nm (ε37,000; 38,000)

Analysis: Calcd for C47 H67 N3 O3 : C, 70.4; H, 8.4; N, 5.2. Found: C, 70.2; H, 8.4; N, 5.1.

EXAMPLE 64 2,4-Bis(5-hexyl-4-hexyloxy-2-hydroxyphenyl)-6-phenyl-s-triazine

To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser, dropping funnel and a nitrogen atmosphere are charged 16.2 g (30 mmol) of the product of Example 62, 3.7 g (66 mmol) of powdered potassium hydroxide and 100 mL of 2-ethoxyethanol. To the resulting red solution are then added 10.9 g (66 mmol) of 1-bromohexane are added dropwise over 30 minutes. The mixture is heated to 90° C. for 20 hours and filtered hot. The filtrate is warmed to 100° C. and 1 mL of acetic acid is added. The solution is cooled to 0° C. to give a precipitate. The crude yellow product is recrystallized from 70 mL of 2-ethoxyethanol to give the title compound in a yield of 13.1 g as a yellow solid melting at 118°-121° C.

1 H nmr (CDCl3) spectrum is consistent with the desired product; UV λmax (chloroform) 301; 371 nm (ε33,000; 40,000)

Analysis: Calcd for C45 H63 N3 O4 : C, 76.1; H, 8.9; N, 5.9. Found: C, 76.2; H, 8.9; N, 5.9.

EXAMPLE 65 2-[2,4-Dihydroxy-5-(1-propenyl)phenyl]-4,6-bis-(2,4-dimethylphenyl)-s-triazine

To a 100 mL round-bottomed, three-necked flask equipped with a magnetic stirrer, condenser, dropping funnel and a nitrogen atmosphere are charged 410 mg(10.0 mmol) of sodium borohydride and 30 mL of anhydrous ethanol. A solution of 500 mg (1.1 mmol) of the product of Example 12 in 10 mL of ethanol is added dropwise over a 35 minute period. The mixture is heated to 68° C. and stirred for three hours. The mixture is allowed to cool to room temperature and is quenched with 10 mL of 2M hydrochloric acid. A portion of ethyl acetate is added and the layers separated. The organic layer is dried over anhydrous magnesium sulfate, filtered and the solvent removed under reduced pressure. The crude product is purified with medium pressure chromatography with 3:1 heptane:ethyl acetate to afford 34 mg of the title compound as a yellow solid.

1 H nmr (CDCl3), infrared and mass spectra are consistent with the desired compound; UV λmax (ethyl acetate) 286; 352 nm (ε44,000; 12,500).

EXAMPLE 66 Delamination Resistance of High Solids Thermoset Acrylic Clear Coats Containing UV Absorbers Applied over UV Transparent Base Coats

Test panels are prepared by spray applying a 1.8 -2.0 mil (0.036 -0.05 1 mm) thick film of a commercially available high solids thermoset acrylic melamine clear coat, containing 2% by weight, based on the acrylic melamine resin, of a test UV absorber stabilizer of this invention, over a commercially available UV transparent base coat, wet-on-wet. The topcoat is applied over 4"×12" (10.16 cm×30.48 cm) UNIPRIME® panels obtained from Advance Coatings Technology, Inc. The coated panels are then baked at 250° F. (121° C.) for 30 minutes. After storage for one week in an air-conditioned room, the panels are exposed in Florida at 5° South, black box according to SAE J-1976. The panels are exposed for one year. After one year, a humidity test is conducted consisting of exposing the panels to 100° F. (38° C.) and 100% humidity for four days. After four days, a tape adhesion test is performed.

The instant compounds are effective in improving adhesion of the clear coat to the base coat during weathering.

EXAMPLE 67 Delamination Resistance of Acrylic Urethane Clear Coats Containing UV Absorbers Applied Directly over Electrocoat Primer

Test panels are prepared by spray applying a 1.8 -2.0 mil (0.036 -0.05 1 mm) thick film of a commercially available acrylic urethane clear coat, containing 2% by weight, based on the acrylic urethane resin, of a test UV absorber stabilizer of this invention, directly over 4"×12" (10.16 cm×30.48 cm) UNIPRIME® panels obtained from Advance Coatings Technology, Inc. The coated panels are then baked at 250° F. (121° C.) for 30 minutes. After storage for one week in an air-conditioned room, the panels are exposed in Florida at 5° South, black box according to SAE J-1976. The panels are evaluated every day for delamination and are retired from the test when delamination is evident over 10% of the panel area.

The instant compounds are effective in delaying delamination of the clear coat from the electrocoat primer.

EXAMPLE 68

The following example demonstrates the utility of the o-hydroxyphenyl-s-triazines of the instant invention in a laminated polycarbonate plaque wherein the UV absorber is incorporated only into the thin surface protecting layer such as prepared in a coextruded article.

Laminated plaques are prepared by bonding a 1 mil (0.0254 mm) polycarbonate film (LEXAN® 141-111N), General Electric Co.) containing 5% by weight of an UV absorber to a non-UV stabilized 125 mil (3.18 mm) polycarbonate plaque (LEXAN® 141-11l N) via compression molding in a Wabash Compression molder at 350° F. (177° C.) for three minutes at 1000 psi (70 Kg/cm2), three minutes at 3000 psi (210 Kg/cm2), and then three minutes at 3000 psi (210 Kg/cm2) while cooling. The plaques are then exposed in an Atlas CI-65 Xenon Arc Weatherometer, using the ASTM designation G26 -88 Test Method C with the protective layer facing the incident light. Polymer degradation is determined by measuring yellowness index (YI) on an ACS spectrophotometer.

The o-hydroxyphenyl-s-triazines of the instant invention are very effective in protecting the polycarbonate sheet from degradation and discoloration.

EXAMPLE 69

Polypropylene fiber samples are prepared by extruding fiber grade polypropylene containing a pigment, a phosphite, a phenolic antioxidant or hydroxylamine, a metal stearate, a UV absorber or hindered amine light stabilizer or a combination of a UV absorber and hindered amine light stabilizer.

The pigment is added as a pigment concentrate which is prepared from pure pigment and polypropylene resin (PROFAX® 6301, Himont) by mixing the two components in a high shear mixer in a ratio of 25% pigment and 75% resin, pressing the resulting resin/pigment mixture on a Wabash Compression Molder (Model #30-1515-4T3) into a thin sheet and then dividing the sheet into fine chips for dispersion in fresh polypropylene resin at reduced concentrations.

All additive and pigment concentrations in the final formulations are expressed as weight percent based on the resin.

The formulations contain 0.05 -0.1% phosphite, 0 -1.25% phenolic antioxidant, 0 -0.1% hydroxylamine, 0.05 -0.1% calcium stearate, 0 -1.25% UV absorber of this invention and/or 0 -1.25% hindered amine stabilizer. The materials are dry-blended in a tumble dryer, extruded on a Superior/MPM 1" (2.54 cm) single screw extruder with a general all-purpose screw (24:1 L/D) at 475° F. (246° C.), cooled in a water bath and pelletized. The resulting pellets are spun into fiber at about 525° F. (274° C.) on a HILLS Research Fiber Extruder (Model #REM-3P-24) fitted with a 41 hole, delta configuration spinnerette. The spun tow is stretched at a draw ratio of 3.2:1 producing a final denier of 615/41.

The fiber samples are knitted into socks on a Lawson-Hemphill Fiber Analysis Knitter, cut into appropriate lengths and exposed in an Atlas Ci65 Xenon Arc Weather-Ometer at 89° C. black panel temperature, 0.55 W/m2 at 340 nanometers and 50% relative humidity (Society of Automotive Engineers SAE J 1885 Test Procedure).

Fiber samples are tested by performing color measurements on an Applied Color Systems spectrophotometer by reflectance mode according to ASTM D 2244-79 at regular intervals. Identical, but separate, samples are examined for catastrophic failure.

While the UV absorbers of this invention do not adequately protect the pigmented polypropylene fiber from actinic induced degradation when used in the absence of a hindered amine, the combination of a UV absorber of this invention with a hindered amine provides far superior protection to the pigmented polypropylene fiber, indeed synergistic stabilization protection over the level of protection provided by the hindered amine alone when used at the same total concentration.

The same superior stabilization is seen when the pigmented polypropylene fiber is replaced with pigmented nylon or polyester fiber.

Claims (3)

What is claimed is:
1. A process for the preparation of a compound of formula I ##STR11## where R1 is straight or branched chain alkyl of 4 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 8 to 15 carbon atoms,
R2 is hydrogen, and
X and Y are the same or different and are phenyl or phenyl substituted by 1 to 3 lower alkyl or by 1 to 3 chloro groups, which comprises reacting a compound of formula A ##STR12## where R2, X and Y are as defined above, with a two to ten excess equivalent amount of an alkene of 4 to 24 carbon atoms, a cycloalkene of 5 to 12 carbon atoms or an phenylalkene of 8 to 15 carbon atoms, compared to the amount of the compound of formula A neat in the presence of a catalytic amount of a Friedel-Crafts alkylation catalyst at a temperature of 110° C. to 250° C.
2. A process according to claim 1 wherein the catalyst is aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, diisobutylaluminum hydride or aluminum isopropoxide.
3. A process according to claim 2 wherein the catalyst is aluminum isopropoxide.
US08463140 1994-07-27 1995-06-02 Red-shifted tris-aryl-s-triazines and compositions stabilized therewith Expired - Lifetime US5543518A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US08281381 US5556973A (en) 1994-07-27 1994-07-27 Red-shifted tris-aryl-s-triazines and compositions stabilized therewith
US08463140 US5543518A (en) 1994-07-27 1995-06-02 Red-shifted tris-aryl-s-triazines and compositions stabilized therewith

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US08463140 US5543518A (en) 1994-07-27 1995-06-02 Red-shifted tris-aryl-s-triazines and compositions stabilized therewith

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US08281381 Division US5556973A (en) 1994-07-27 1994-07-27 Red-shifted tris-aryl-s-triazines and compositions stabilized therewith

Publications (1)

Publication Number Publication Date
US5543518A true US5543518A (en) 1996-08-06

Family

ID=23077052

Family Applications (7)

Application Number Title Priority Date Filing Date
US08281381 Expired - Lifetime US5556973A (en) 1994-07-27 1994-07-27 Red-shifted tris-aryl-s-triazines and compositions stabilized therewith
US08463573 Expired - Lifetime US5648488A (en) 1994-07-27 1995-06-02 Compositions stabilized with red-shifted tris-aryl-s-triazines
US08463572 Expired - Lifetime US5637706A (en) 1994-07-27 1995-06-02 Compositions stabilized with red-shifted tris-aryl-s-triazines
US08463140 Expired - Lifetime US5543518A (en) 1994-07-27 1995-06-02 Red-shifted tris-aryl-s-triazines and compositions stabilized therewith
US08463569 Expired - Lifetime US5675004A (en) 1994-07-27 1995-06-02 Red-shifted tris-aryl-S-triazines
US08680730 Expired - Fee Related US5684070A (en) 1994-07-27 1996-07-15 Compositions stabilized with red-shifted tris-aryl-s-triazines
US08680732 Expired - Fee Related US5681955A (en) 1994-07-27 1996-07-15 Red-shifted tris-aryl-s-triazines

Family Applications Before (3)

Application Number Title Priority Date Filing Date
US08281381 Expired - Lifetime US5556973A (en) 1994-07-27 1994-07-27 Red-shifted tris-aryl-s-triazines and compositions stabilized therewith
US08463573 Expired - Lifetime US5648488A (en) 1994-07-27 1995-06-02 Compositions stabilized with red-shifted tris-aryl-s-triazines
US08463572 Expired - Lifetime US5637706A (en) 1994-07-27 1995-06-02 Compositions stabilized with red-shifted tris-aryl-s-triazines

Family Applications After (3)

Application Number Title Priority Date Filing Date
US08463569 Expired - Lifetime US5675004A (en) 1994-07-27 1995-06-02 Red-shifted tris-aryl-S-triazines
US08680730 Expired - Fee Related US5684070A (en) 1994-07-27 1996-07-15 Compositions stabilized with red-shifted tris-aryl-s-triazines
US08680732 Expired - Fee Related US5681955A (en) 1994-07-27 1996-07-15 Red-shifted tris-aryl-s-triazines

Country Status (6)

Country Link
US (7) US5556973A (en)
EP (1) EP0704437B1 (en)
JP (1) JP3965603B2 (en)
CA (1) CA2154626A1 (en)
DE (2) DE69528331T2 (en)
ES (1) ES2181760T3 (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2317174A (en) * 1996-09-13 1998-03-18 Ciba Geigy Ag Hydroxyphenytriazine stabilisers
US6225468B1 (en) 1998-09-04 2001-05-01 Cytec Technology Corp. Process for making 2-(2,4,-dihydroxyphenyl) or 2-(2,4-dialkoxyphenyl)-4,6-bisaryl-1,3,5-triazines
US6242597B1 (en) 1997-11-21 2001-06-05 Ciba Specialty Chemicals Corporation Trisaryl-1,3,5-triazine ultraviolet light absorbers
US6297377B1 (en) 1998-06-22 2001-10-02 Cytec Technology Corporation Benzocycle-substituted triazine and pyrimidine ultraviolet light absorbers
US6486317B1 (en) 1998-09-04 2002-11-26 Ciba Specialty Chemicals Corporation Process for making 2-hydroxy-4-alkoxyphenyl or 2,4-dihydroxyphenyl substituted 1,3,5-triazine UV absorbers
US6486316B1 (en) 1998-11-17 2002-11-26 Cytec Technology Corp. Process for making triazine UV absorbers using Lewis acids and reaction promoters
WO2004076419A1 (en) 2003-02-26 2004-09-10 Ciba Specialty Chemicals Holding Inc. Water compatible sterically hindered alkoxyamines and hydroxy substituted alkoxyamines
US20100062270A1 (en) * 2007-01-15 2010-03-11 Ciba Corporation Tinted clear coatings uv stabilized with 2-hydroxy phenyl triazine
WO2010072592A1 (en) 2008-12-22 2010-07-01 Basf Se Method of improving scratch resistance and related products and uses
EP2267523A2 (en) 2004-07-12 2010-12-29 Basf Se Stabilized electrochromic media
EP2450401A1 (en) 2008-09-05 2012-05-09 THOR GmbH Flame-resistant compound containing a phosphoric acid derivative
US20120136098A1 (en) * 2009-07-29 2012-05-31 Fujifilm Corporation New triazine derivative, ultraviolet absorber, and resin composition
US8399536B2 (en) 2007-06-29 2013-03-19 Basell Poliolefine Italia, s.r.l. Irradiated polyolefin composition comprising a non-phenolic stabilizer
WO2015044785A2 (en) 2013-09-27 2015-04-02 Basf Se Polyolefin compositions for building materials
WO2015077635A2 (en) 2013-11-22 2015-05-28 Polnox Corporation Macromolecular antioxidants based on dual type moiety per molecule: structures methods of making and using the same
WO2017013028A1 (en) 2015-07-20 2017-01-26 Basf Se Flame retardant polyolefin articles

Families Citing this family (173)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2879756B2 (en) * 1993-12-02 1999-04-05 カシオ計算機株式会社 The printer device
DE69633927T2 (en) * 1995-08-30 2005-11-24 Cytec Technology Corp., Wilmington Compositions containing 1,3,5-triazine carbamates and epoxy compounds
US5759689A (en) * 1996-06-13 1998-06-02 General Electric Company Coextruded polycarbonate sheet with improved weathering
US5726309A (en) * 1996-08-27 1998-03-10 Ciba Specialty Chemicals Corporation Tris-aryls-triazines substituted with biphenylyl groups
BE1012529A3 (en) * 1996-09-13 2000-12-05 Ciba Sc Holding Ag Triaryltriazines mixing and its use for the stabilization of organic materials.
EP0931104A1 (en) * 1996-10-08 1999-07-28 Cytec Technology Corp. Crosslinker compositions and low gloss epoxy coatings therefrom
GB2319523B (en) 1996-11-20 2000-11-08 Ciba Sc Holding Ag Hydroxyphenyltriazines
US6117997A (en) * 1997-11-19 2000-09-12 Ciba Specialty Chemicals Corporation Hydroxyphenyltriazines
US5985251A (en) * 1997-12-01 1999-11-16 Roche Vitamins Inc. Light screening compositions
US6018044A (en) * 1998-01-02 2000-01-25 Roche Vitamins Inc. Light screening compositions
EP0941989B1 (en) * 1998-03-02 2009-07-08 Ciba Holding Inc. Process for the preparation of 2,4-diaryl-6-o-hydroxyphenyl-1,3,5-triazine derivatives in the presence of a protic acid catalyst
JP2000026435A (en) * 1998-05-07 2000-01-25 Ciba Specialty Chem Holding Inc Trisresorcinyltriazine
ES2238839T3 (en) * 1998-06-22 2005-09-01 Ciba Specialty Chemicals Holding Inc. Ultraviolet light absorbers poly-trisaryl-1,3,5-triazine.
JP2002518487A (en) * 1998-06-22 2002-06-25 サイテク・テクノロジー・コーポレーシヨン Benzo ring substituted triazine and pyrimidine ultraviolet absorber
US6239276B1 (en) 1998-06-22 2001-05-29 Cytec Technology Corporation Non-yellowing para-tertiary-alkyl phenyl substituted triazine and pyrimidine ultraviolet light absorbers
CA2336246A1 (en) * 1998-06-22 1999-12-29 Cytec Technology Corp. Red-shifted trisaryl-1,3,5-triazine ultraviolet light absorbers
US6187374B1 (en) 1998-09-02 2001-02-13 Xim Products, Inc. Coatings with increased adhesion
WO2000061685A1 (en) * 1999-04-12 2000-10-19 Asahi Denka Kogyo K. K. Polymeric material composition
US6191199B1 (en) 1999-05-03 2001-02-20 Ciba Speciatly Chemicals Corporation Stabilized adhesive compositions containing highly soluble, high extinction photostable hydroxyphenyl-s-triazine UV absorbers and laminated articles derived therefrom
CA2396221C (en) 2000-02-01 2010-03-23 Ciba Specialty Chemicals Holding Inc. Method of content protection with durable uv absorbers
CA2406255C (en) 2000-05-19 2010-12-21 Ciba-Specialty Chemicals Holding Inc. Hydroxylamine esters as polymerization initiators
US6409017B1 (en) * 2000-06-30 2002-06-25 Corning Incorporated Use of inhibitor in optical fiber reel covers
CA2352708C (en) * 2000-07-26 2011-10-18 Ciba Specialty Chemicals Holding Inc. Transparent polymer articles of low thickness
US6867250B1 (en) 2000-10-30 2005-03-15 Cytec Technology Corp. Non-yellowing ortho-dialkyl aryl substituted triazine ultraviolet light absorbers
DE60219447D1 (en) 2001-03-22 2007-05-24 Ciba Sc Holding Ag Use of aromatic compounds as medium to control the phase and for reducing the particle size of quinacridone pigments
US6855269B2 (en) * 2001-11-09 2005-02-15 Cytec Technology Corp. Phenyl ether-substituted hydroxyphenyl triazine ultraviolet light absorbers
US7214742B2 (en) * 2001-11-30 2007-05-08 Ciba Specialty Chemicals Corp. 2-hydroxyphenyl-s-triazine crosslinkers for polymer networks
WO2003057772A3 (en) * 2001-12-27 2004-06-03 Cytec Tech Corp Uv stabilized thermoplastic olefins
US6878761B2 (en) * 2002-03-04 2005-04-12 Ciba Specialty Chemicals Corp. Synergistic combinations of UV absorbers for pigmented polyolefins
JP4486810B2 (en) 2003-01-08 2010-06-23 富士フイルム株式会社 Coloring composition and an ink jet recording method
DE60306203D1 (en) * 2003-01-09 2006-07-27 Alcon Inc lentils dual function UV absorber materials for ophthalmic
DE602004029677D1 (en) 2003-06-18 2010-12-02 Fujifilm Corp Ink and ink jet printing ink
CN1860167B (en) 2003-09-29 2011-01-26 西巴特殊化学品控股有限公司 Stabilization of photochromic systems
EP2436740A1 (en) 2003-09-29 2012-04-04 Fujifilm Corporation Ink for inkjet printing, ink set for inkjet printing, inkjet recording material and producing method for inkjet recording material, and inkjet recording method
KR20060094530A (en) 2003-10-23 2006-08-29 후지 샤신 필름 가부시기가이샤 Ink and ink set for inkjet recording
EP1914594A3 (en) 2004-01-30 2008-07-02 FUJIFILM Corporation Silver halide color photographic light-sensitive material and color image-forming method
US7732504B2 (en) 2004-02-02 2010-06-08 Ciba Specialty Chemicals Corporation Functionalized photoinitiators
JP2005320517A (en) * 2004-04-06 2005-11-17 Matsushita Electric Works Ltd Coating composition, substrate with coating film, illuminator and lamp
US20060204732A1 (en) 2005-03-08 2006-09-14 Fuji Photo Film Co., Ltd. Ink composition, inkjet recording method, printed material, method of producing planographic printing plate, and planographic printing plate
DE102005012056A1 (en) * 2005-03-16 2006-09-28 Basf Coatings Ag Multi-layer coatings, processes for their preparation and their use in the automotive industry
US20090117394A1 (en) * 2005-06-10 2009-05-07 Thomas Vogel Tris(Hydroxyphenyl) Triazines
ES2439917T3 (en) * 2005-06-10 2014-01-27 Basf Se Hydroxyphenyltriazines a fused ring system carbocyclic aromatic
JP4662822B2 (en) 2005-07-19 2011-03-30 富士フイルム株式会社 Photocurable inkjet recording apparatus
JP4677306B2 (en) 2005-08-23 2011-04-27 富士フイルム株式会社 Ink-jet recording device
EP1757635B1 (en) 2005-08-23 2008-10-08 FUJIFILM Corporation Curable ink comprising modified oxetane compound
JP4757574B2 (en) 2005-09-07 2011-08-24 富士フイルム株式会社 The ink composition, inkjet recording method, printed material, method of manufacturing a lithographic printing plate, and lithographic printing plate
US7728050B2 (en) 2005-11-04 2010-06-01 Fujifilm Corporation Curable composition, ink composition, inkjet recording method, printed matter, method for producing planographic printing plate, planographic printing plate and oxetane compound
DE602007012161D1 (en) 2006-03-03 2011-03-10 Fujifilm Corp Curable composition, ink composition, inkjet recording method and lithographic printing plate
JP4719606B2 (en) 2006-03-30 2011-07-06 富士フイルム株式会社 The ink jet head recording apparatus
JPWO2007139033A1 (en) 2006-05-26 2009-10-08 富士フイルム株式会社 Surface-emitting electroluminescent device
JP5215538B2 (en) 2006-06-30 2013-06-19 富士フイルム株式会社 Azo dyes, coloring composition, a thermal transfer recording ink sheet, a thermal transfer recording method, a color toner, an inkjet ink and a color filter
JP5276264B2 (en) 2006-07-03 2013-08-28 富士フイルム株式会社 The ink composition, inkjet recording method, printed material, and method of manufacturing a lithographic printing plate
US8092909B2 (en) * 2006-09-07 2012-01-10 Columbia Insurance Company Color foundation coat and color top coat paint system
JP2008189776A (en) 2007-02-02 2008-08-21 Fujifilm Corp Active radiation-curable polymerizable composition, ink composition, inkjet recording method, printed matter, preparation method of lithographic printing plate, and lithographic printing plate
JP5227521B2 (en) 2007-02-26 2013-07-03 富士フイルム株式会社 The ink composition, inkjet recording method, printed material, and an ink set
JP2008208266A (en) 2007-02-27 2008-09-11 Fujifilm Corp Ink composition, inkjet recording method, printed material, method for producing planographic printing plate, and planographic printing plate
JP5224699B2 (en) 2007-03-01 2013-07-03 富士フイルム株式会社 The ink composition, inkjet recording method, printed material, method of manufacturing a lithographic printing plate, and planographic printing plate
JP2010520863A (en) * 2007-03-02 2010-06-17 ザ ユニバーシティー オブ テネシー リサーチ ファウンデーション Triaryl / heteroaromatic cannabinoids and their use
EP1970196A3 (en) 2007-03-13 2010-01-27 FUJIFILM Corporation Hydrophilic member and process for producing the same
WO2008110487A1 (en) 2007-03-15 2008-09-18 Basf Se Heat-sensitive coating compositions based on resorcinyl triazine derivatives
EP1974948A3 (en) 2007-03-29 2012-02-08 FUJIFILM Corporation Image-forming method using heat-sensitive transfer system
EP1980409A3 (en) 2007-03-29 2010-09-29 FUJIFILM Corporation Heat-sensitive transfer sheet for use in heat-sensitive transfer system and image-forming method using heat-sensitive transfer system
JP2008246793A (en) 2007-03-29 2008-10-16 Fujifilm Corp Active energy ray curable inkjet recorder
US8119562B2 (en) 2007-03-29 2012-02-21 Fujifilm Corporation Heat-sensitive transfer sheet and image-forming method using heat-sensitive transfer system
JP2008248124A (en) 2007-03-30 2008-10-16 Fujifilm Corp Colored composition, ink sheet for heat-sensitive transfer recording, heat-sensitive transfer recording method, color toner, ink-jet ink, color filter and azo pigment
JP5159141B2 (en) 2007-03-30 2013-03-06 富士フイルム株式会社 The ink composition, inkjet recording method, printed material, manufacturing method and a lithographic printing plate of a lithographic printing plate
JP2008273641A (en) 2007-04-25 2008-11-13 Fujifilm Corp Cardboard cylinder for heat-sensitive transfer image-receiving sheet, roll shape machined article and image forming method of the sheet
JP5337394B2 (en) 2007-05-15 2013-11-06 富士フイルム株式会社 The hydrophilic coating composition and a hydrophilic member using the same
US7951854B2 (en) 2007-06-08 2011-05-31 Fujifilm Corporation Ink composition, ink set and inkjet recording method
EP2167323B1 (en) 2007-07-18 2018-04-04 DataLase Ltd Laser-sensitive coating formulation
JP5213382B2 (en) 2007-08-09 2013-06-19 富士フイルム株式会社 The aqueous ink composition, an ink set, and an image recording method
JP2009256568A (en) 2007-08-17 2009-11-05 Fujifilm Corp Hydrophilic film-forming composition, spray composition, and hydrophilic member using the same
CN101784620B (en) 2007-08-22 2013-05-29 巴斯夫欧洲公司 Laser-sensitive coating composition
JP5469837B2 (en) 2007-09-12 2014-04-16 富士フイルム株式会社 Hydrophilic composition
JP2009090641A (en) 2007-09-20 2009-04-30 Fujifilm Corp Anticlouding cover and cover for meter using it
JP2009256564A (en) 2007-09-26 2009-11-05 Fujifilm Corp Composition for formation of hydrophilic film, and hydrophilic member
US8076393B2 (en) 2007-09-26 2011-12-13 Fujifilm Corporation Ink composition, inkjet recording method, and printed material
JP5111039B2 (en) 2007-09-27 2012-12-26 富士フイルム株式会社 Polymerizable compound, a polymerization initiator, and photo-curable composition containing a dye
JP5236238B2 (en) 2007-09-28 2013-07-17 富士フイルム株式会社 Jet recording white ink composition
JP5227560B2 (en) 2007-09-28 2013-07-03 富士フイルム株式会社 The ink composition, inkjet recording method, printed material, and a method for producing molded printed material
JP2009084494A (en) 2007-10-01 2009-04-23 Fujifilm Corp Aqueous colorant dispersion, method of producing aqueous colorant dispersion, and aqueous ink for inkjet recording
JP2009090489A (en) 2007-10-04 2009-04-30 Fujifilm Corp Image forming method and image forming apparatus
WO2009059888A1 (en) 2007-11-07 2009-05-14 Basf Se New fiber products
JP4642892B2 (en) 2007-11-09 2011-03-02 富士フイルム株式会社 Pigment compositions, aqueous pigment dispersion, a method of manufacturing a water-based pigment dispersion, a water-based ink for inkjet recording
JP5201954B2 (en) 2007-11-19 2013-06-05 富士フイルム株式会社 Ink jet recording recording medium and a manufacturing method thereof and an inkjet recording method,
JP5201955B2 (en) 2007-11-19 2013-06-05 富士フイルム株式会社 Ink jet recording recording medium and a manufacturing method thereof and an inkjet recording method,
US8240838B2 (en) 2007-11-29 2012-08-14 Fujifilm Corporation Ink composition for inkjet recording, inkjet recording method, and printed material
JP5124496B2 (en) 2008-02-01 2013-01-23 富士フイルム株式会社 Hydrophilic member
JP5591473B2 (en) 2008-02-05 2014-09-17 富士フイルム株式会社 The ink composition, inkjet recording method, and printed material
JP5383225B2 (en) 2008-02-06 2014-01-08 富士フイルム株式会社 The ink composition, inkjet recording method, and printed material
JP5254632B2 (en) 2008-02-07 2013-08-07 富士フイルム株式会社 The ink composition, inkjet recording method, printed material, and, molded printed material
JP5079538B2 (en) 2008-02-13 2012-11-21 富士フイルム株式会社 Jet recording ink set and an image recording method
US20090214797A1 (en) 2008-02-25 2009-08-27 Fujifilm Corporation Inkjet ink composition, and inkjet recording method and printed material employing same
JP2009226781A (en) 2008-03-24 2009-10-08 Fujifilm Corp Method of forming inkjet image
JP2009227909A (en) 2008-03-25 2009-10-08 Fujifilm Corp Ink set for inkjet, image recording method, and image recorder
JP2009233867A (en) 2008-03-25 2009-10-15 Fujifilm Corp Inkjet recording method and recorded matter
JP2009235113A (en) 2008-03-25 2009-10-15 Fujifilm Corp Method for forming inkjet image
JP5427382B2 (en) 2008-03-25 2014-02-26 富士フイルム株式会社 Hydrophilic member, fin material, aluminum fin stock, heat exchanger and air conditioning
JP4914862B2 (en) 2008-03-26 2012-04-11 富士フイルム株式会社 The ink jet recording method, and inkjet recording apparatus
JP5568222B2 (en) 2008-06-16 2014-08-06 富士フイルム株式会社 The ink composition, inkjet recording ink composition, ink set, ink cartridge, inkjet recording method and recorded matter
US8523990B2 (en) 2008-06-16 2013-09-03 Fujifilm Corporation Ink composition, inkjet recording ink composition, ink set, ink cartridge, inkjet recording method and recorded matter
JP2010030223A (en) 2008-07-30 2010-02-12 Fujifilm Corp Inkjet recording method, inkjet recorder, and printed matter
JP2010069805A (en) 2008-09-19 2010-04-02 Fujifilm Corp Ink set and inkjet recording method
JP5383133B2 (en) 2008-09-19 2014-01-08 富士フイルム株式会社 Ink compositions, method for producing an ink jet recording method and printed formed product
JP2010077228A (en) 2008-09-25 2010-04-08 Fujifilm Corp Ink composition, inkjet recording method and printed material
EP2169018B1 (en) 2008-09-26 2012-01-18 Fujifilm Corporation Ink composition and inkjet recording method
JP2010077285A (en) 2008-09-26 2010-04-08 Fujifilm Corp Ink set and method for forming image
JP5461809B2 (en) 2008-09-29 2014-04-02 富士フイルム株式会社 The ink composition and ink jet recording method
KR101691898B1 (en) 2008-10-23 2017-01-02 데이터레이즈 리미티드 Heat absorbing additives
EP2342295A1 (en) 2008-10-27 2011-07-13 DataLase Ltd Coating composition for marking substrates
JP5645832B2 (en) 2008-10-27 2014-12-24 データレース リミテッドDatalase Ltd. Laser-sensitive aqueous composition for marking substrates
JP5344892B2 (en) 2008-11-27 2013-11-20 富士フイルム株式会社 Inkjet ink composition, and an inkjet recording method
EP2385937A1 (en) 2009-01-08 2011-11-16 Basf Se Polymerisation initiator
KR101773621B1 (en) 2009-01-19 2017-08-31 바스프 에스이 Organic black pigments and their preparation
JP5225156B2 (en) 2009-02-27 2013-07-03 富士フイルム株式会社 Radiation-curable ink composition for inkjet recording, an inkjet recording method and printed material
JP2010202756A (en) 2009-03-03 2010-09-16 Fujifilm Corp Active energy ray-curable ink composition, inkjet recording method, and printed matter
US8097688B2 (en) 2009-03-09 2012-01-17 Fujifilm Corporation Ink composition and inkjet recording method
JP5349095B2 (en) 2009-03-17 2013-11-20 富士フイルム株式会社 The ink composition and ink jet recording method
JP5349097B2 (en) 2009-03-19 2013-11-20 富士フイルム株式会社 The ink composition, inkjet recording method, printed material, and a method for producing molded printed material
JP2010229349A (en) 2009-03-27 2010-10-14 Fujifilm Corp Active energy ray-curable composition, active energy ray-curable ink composition and inkjet recording method
WO2010112410A1 (en) 2009-03-30 2010-10-07 Basf Se Polymerizable compositions
JP5405174B2 (en) 2009-03-30 2014-02-05 富士フイルム株式会社 Ink composition
JP5383289B2 (en) 2009-03-31 2014-01-08 富士フイルム株式会社 The ink composition, the ink composition is an inkjet printed matter by an inkjet recording method, and inkjet method
JP5579533B2 (en) 2009-08-27 2014-08-27 富士フイルム株式会社 The novel oxetane compound, an active energy ray-curable composition, an active energy ray-curable ink composition, and an inkjet recording method
JP5583376B2 (en) 2009-09-15 2014-09-03 富士フイルム株式会社 Inkjet ink composition
JP5572026B2 (en) 2009-09-18 2014-08-13 富士フイルム株式会社 The ink composition and ink jet recording method
JP2011068783A (en) 2009-09-25 2011-04-07 Fujifilm Corp Ink composition and inkjet recording method
JP5489616B2 (en) 2009-09-28 2014-05-14 富士フイルム株式会社 Method for producing an ink composition and printed molded
JP5448924B2 (en) 2010-02-25 2014-03-19 富士フイルム株式会社 The ink composition, ink set, and an image forming method using the same
JP5448934B2 (en) 2010-03-01 2014-03-19 富士フイルム株式会社 The ink composition, ink set, and an image forming method using the same
JP2011202144A (en) * 2010-03-01 2011-10-13 Fujifilm Corp Adhesive composition, adhesive tape or film using the same, surface protective film, laminated glass and solar cell module
JP5538964B2 (en) 2010-03-16 2014-07-02 富士フイルム株式会社 The ink composition, ink set, and an image forming method using the same
JP5371844B2 (en) 2010-03-16 2013-12-18 富士フイルム株式会社 Treatment liquid, ink set and image forming method
JP5566745B2 (en) 2010-03-26 2014-08-06 富士フイルム株式会社 The ink composition, ink set, and an image forming method
JP5554114B2 (en) 2010-03-29 2014-07-23 富士フイルム株式会社 Radiation-curable inkjet ink composition, printed material, methods for producing printed material, printed formed, and a manufacturing method of the printed formed product
JP5496739B2 (en) 2010-03-30 2014-05-21 富士フイルム株式会社 The image forming method
US8573765B2 (en) 2010-03-31 2013-11-05 Fujifilm Corporation Active radiation curable ink composition, ink composition for inkjet recording, printed matter, and method of producing molded article of printed matter
US8746865B2 (en) 2010-03-31 2014-06-10 Fujifilm Corporation Image forming method
JP5813352B2 (en) 2010-04-09 2015-11-17 富士フイルム株式会社 The ink composition and its manufacturing method, an ink set, and an image forming method
JP5518588B2 (en) 2010-06-17 2014-06-11 富士フイルム株式会社 Ink set, and an image forming method
JP5606817B2 (en) 2010-07-27 2014-10-15 富士フイルム株式会社 Radiation-curable inkjet ink composition, printed matter, printed formed product, and methods for producing printed material
JP5785799B2 (en) 2010-07-30 2015-09-30 富士フイルム株式会社 The novel azo compounds, an aqueous solution, the ink composition, inkjet recording ink, inkjet recording method, inkjet recording ink cartridge, and ink-jet recorded matter
JP5866150B2 (en) 2010-07-30 2016-02-17 富士フイルム株式会社 The novel azo compounds, an aqueous solution, the ink composition, inkjet recording ink, inkjet recording method, inkjet recording ink cartridge, and ink-jet recorded matter
JP5850654B2 (en) 2010-12-28 2016-02-03 富士フイルム株式会社 Jet recording ink
EP3124557A1 (en) 2011-02-28 2017-02-01 Fujifilm Corporation Ink composition, image forming method, and printed matter
JP2012211293A (en) 2011-03-18 2012-11-01 Fujifilm Corp Ink composition, inkjet recording ink, and inkjet recording method
JP2012201874A (en) 2011-03-28 2012-10-22 Fujifilm Corp Ink composition, and method of forming image
JP5696004B2 (en) 2011-08-30 2015-04-08 富士フイルム株式会社 Novel compounds having triazine side chain, colored composition, an inkjet ink, an inkjet recording method, a color filter, and a color toner
CN103842449B (en) 2011-09-29 2015-12-23 富士胶片株式会社 The inkjet ink composition and an ink jet recording method
JP5667955B2 (en) 2011-09-29 2015-02-12 富士フイルム株式会社 Novel triazine derivatives, UV absorbers
KR101717829B1 (en) 2011-11-08 2017-03-17 후지필름 가부시키가이샤 Coloured composition and ink for inkjet recording
WO2013099677A1 (en) 2011-12-26 2013-07-04 富士フイルム株式会社 Compound having xanthene skeleton, coloring composition, ink for ink jet printing, and ink jet printing method
WO2013103139A1 (en) 2012-01-06 2013-07-11 コニカミノルタアドバンストレイヤー株式会社 Film mirror, film mirror manufacturing method, film mirror for photovoltaic power generation, and reflection device for photovoltaic power generation
CN104144986A (en) 2012-02-29 2014-11-12 富士胶片株式会社 Colored composition, inkjet recording ink, and inkjet recording method
JP5666498B2 (en) 2012-03-22 2015-02-12 富士フイルム株式会社 The ink composition, ink set, and image forming method
JP5836200B2 (en) 2012-05-30 2015-12-24 富士フイルム株式会社 A compound having a xanthene skeleton, coloring composition, ink for inkjet recording, and an inkjet recording method
EP2669338B1 (en) 2012-05-31 2017-04-05 Fujifilm Corporation Coloring composition, ink for inkjet recording and inkjet recording method
EP2671449A1 (en) 2012-06-06 2013-12-11 Construction Research & Technology GmbH Use of vanadium pentoxide particles as a biocide
JP2014198816A (en) 2012-09-26 2014-10-23 富士フイルム株式会社 Azo compound, aqueous solution, ink composition, ink for inkjet recording, inkjet recording method, ink cartridge for inkjet recording, and inkjet recorded matter
KR101794426B1 (en) 2012-10-23 2017-11-06 바스프 에스이 Iminoxytriazines as radical generators
KR101740166B1 (en) 2012-11-15 2017-05-25 후지필름 가부시키가이샤 Coloring composition, ink jet recording ink using coloring composition, ink jet recording method using ink jet recording ink, ink cartridge, and ink jet recording material
CN104797658A (en) 2012-11-15 2015-07-22 富士胶片株式会社 Coloring composition, ink jet recording ink, ink jet recording method, ink jet printer cartridge, and ink jet recording material
JP5980702B2 (en) 2013-03-07 2016-08-31 富士フイルム株式会社 Inkjet ink composition, inkjet recording method, and a method for producing molded printed material
EP3020566B1 (en) 2013-07-12 2017-03-22 Fujifilm Corporation Image forming method and image recording material
JP5939644B2 (en) 2013-08-30 2016-06-22 富士フイルム株式会社 Image forming method, a method of manufacturing the in-mold molded article, and an ink set
JP6117072B2 (en) 2013-09-30 2017-04-19 富士フイルム株式会社 The pigment dispersion composition, method for producing an ink jet recording method, and compound
JP6170901B2 (en) 2014-01-10 2017-07-26 富士フイルム株式会社 Compounds, coloring composition, ink for inkjet recording, an inkjet recording method, an ink jet printer cartridge, ink jet recording material, color filters, color toners, and transfer ink
JP6169501B2 (en) 2014-01-31 2017-07-26 富士フイルム株式会社 Jet recording ink
EP3178898A4 (en) * 2014-08-05 2018-04-11 Miyoshi Yushi Kk Additive for imparting ultraviolet absorptivity and/or high refractive index to matrix, and resin member using same
JP6169545B2 (en) 2014-09-09 2017-07-26 富士フイルム株式会社 Polymerizable composition, inkjet recording ink composition, inkjet recording method, and recorded matter
JP6086888B2 (en) 2014-09-26 2017-03-01 富士フイルム株式会社 Inkjet recording ink composition, inkjet recording method, and recorded matter
JP6169548B2 (en) 2014-09-26 2017-07-26 富士フイルム株式会社 Polymerizable composition, inkjet recording ink composition, inkjet recording method, and recorded matter
CA2980858A1 (en) 2015-06-02 2016-12-08 Sicpa Holding Sa Processes for producing optical effects layers

Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3118887A (en) * 1961-03-06 1964-01-21 American Cyanamid Co O-hydroxy substituted tris aryl-s-triazines
US3242175A (en) * 1962-10-30 1966-03-22 Ciba Ltd Hydroxyphenyl-1, 3, 5-triazines
US3244708A (en) * 1963-02-07 1966-04-05 Ciba Ltd Hydroxyphenyl-1, 3, 5-triazines
US3268474A (en) * 1961-03-06 1966-08-23 American Cyanamid Co Polymers stabilized with orthohydroxyaryl-s-triazines
US3843371A (en) * 1970-03-23 1974-10-22 Ciba Geigy Ag Photographic material stabilised against the deleterious effects of ultraviolet radiation
EP0165608A2 (en) * 1984-06-22 1985-12-27 Ilford Ag Hydroxyphenyltriazines, process for their preparation and their use as UV absorbers
US4619956A (en) * 1985-05-03 1986-10-28 American Cyanamid Co. Stabilization of high solids coatings with synergistic combinations
US4826978A (en) * 1987-12-29 1989-05-02 Milliken Research Corporation Reactive, non-yellowing triazine compounds useful as UV screening agents for polymers
US4831068A (en) * 1987-02-27 1989-05-16 Ciba-Geigy Corporation Process for improving the photochemical stability of dyeings on polyester fibre materials
US4950304A (en) * 1987-10-02 1990-08-21 Ciba-Geigy Corporation Process for quenching or suppressing the fluorescence of substrates treated with fluorescent whitening agents
US4962142A (en) * 1987-12-29 1990-10-09 Milliken Research Corporation Reactive, non-yellowing triazine compounds useful as UV screening agents for polymers
EP0434608A1 (en) * 1989-12-05 1991-06-26 Ciba-Geigy Ag Stabilized organic material
EP0442847A1 (en) * 1990-02-16 1991-08-21 Ciba-Geigy Ag Coating composition resistant to light, heat and acids
EP0444323A2 (en) * 1990-02-28 1991-09-04 Cytec Technology Corp. Stabilization of high solids coating with liquid compositions of triazine UV absorbers
EP0468921A1 (en) * 1990-07-23 1992-01-29 Ciba-Geigy Ag Aqueous dispersions of slightly soluble UV absorbing agents
US5096489A (en) * 1989-08-25 1992-03-17 Ciba-Geigy Corporation Light-stabilized ink compositions
US5106891A (en) * 1990-03-30 1992-04-21 Ciba-Geigy Corporation Light stabilized coating compositions containing a mixture of 2-hydroxyphenylbenzotriazole and 2-hydroxyphenyltriazine
EP0483488A1 (en) * 1990-10-29 1992-05-06 Cytec Technology Corp. Synergistic ultraviolet absorber compositions containing hydroxy aryl triazines and tetraalkyl piperidines
US5298067A (en) * 1991-02-21 1994-03-29 Ciba-Geigy Corporation Coating materials stabilized against light-induced degradation
GB2273498A (en) * 1992-12-03 1994-06-22 Ciba Geigy Ag S-Triazine UV absorbers

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2042562B (en) 1979-02-05 1983-05-11 Sandoz Ltd Stabilising polymers
US4259467A (en) 1979-12-10 1981-03-31 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains
US4355147A (en) 1981-02-26 1982-10-19 Bausch & Lomb Incorporated Polysiloxane with polycyclic modifier composition and biomedical devices
DE3587925D1 (en) * 1984-12-07 1994-10-13 Commw Scient Ind Res Org Use of sulfonated 2- (2'-hydroxyaryl) -s-triazines as a light stabilizer for wallerand or other protein fibers.
JPH02280462A (en) * 1989-04-20 1990-11-16 Fuji Photo Film Co Ltd Picture data compression method
US5175312A (en) 1989-08-31 1992-12-29 Ciba-Geigy Corporation 3-phenylbenzofuran-2-ones
DE59203628D1 (en) * 1991-05-02 1995-10-19 Ciba Geigy Ag A method for improving the light fastness of leather.
US5252643A (en) 1991-07-01 1993-10-12 Ciba-Geigy Corporation Thiomethylated benzofuran-2-ones
KR100218594B1 (en) 1991-07-01 1999-09-01 Ciba Sc Holding Ag Bis-benzofuran-2-ones
NL9300801A (en) 1992-05-22 1993-12-16 Ciba Geigy 3- (acyloxyphenyl) benzofuran-2-one as stabilizers.
GB2267490B (en) 1992-05-22 1995-08-09 Ciba Geigy Ag 3-(Carboxymethoxyphenyl)benzofuran-2-one stabilisers
NL9300784A (en) 1992-05-22 1993-12-16 Ciba Geigy 3- (alkoxyphenyl) benzofuran-2-ones as stabilizers.
DE69332382T2 (en) * 1992-09-07 2003-06-18 Ciba Sc Holding Ag Hydroxyphenyl-s-triazines
DE59310035D1 (en) 1992-09-23 2000-06-15 Ciba Sc Holding Ag 3- (dihydrobenzofuran-5-yl) benzofuran-2-ones as stabilizers
DE59310117D1 (en) 1992-09-23 2000-11-23 Ciba Sc Holding Ag 3- (2-Acyloxyethoxyphenyl) benzofuran-2-ones as stabilizers
US5354794A (en) 1993-02-03 1994-10-11 Ciba-Geigy Corporation Electro coat/base coat/clear coat finishes stabilized with S-triazine UV absorbers

Patent Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3118887A (en) * 1961-03-06 1964-01-21 American Cyanamid Co O-hydroxy substituted tris aryl-s-triazines
US3268474A (en) * 1961-03-06 1966-08-23 American Cyanamid Co Polymers stabilized with orthohydroxyaryl-s-triazines
US3242175A (en) * 1962-10-30 1966-03-22 Ciba Ltd Hydroxyphenyl-1, 3, 5-triazines
US3244708A (en) * 1963-02-07 1966-04-05 Ciba Ltd Hydroxyphenyl-1, 3, 5-triazines
US3843371A (en) * 1970-03-23 1974-10-22 Ciba Geigy Ag Photographic material stabilised against the deleterious effects of ultraviolet radiation
EP0165608A2 (en) * 1984-06-22 1985-12-27 Ilford Ag Hydroxyphenyltriazines, process for their preparation and their use as UV absorbers
US4619956A (en) * 1985-05-03 1986-10-28 American Cyanamid Co. Stabilization of high solids coatings with synergistic combinations
US4740542A (en) * 1985-05-03 1988-04-26 American Cyanamid Company Stabilization of high solids coatings with synergistic combinations
US4831068A (en) * 1987-02-27 1989-05-16 Ciba-Geigy Corporation Process for improving the photochemical stability of dyeings on polyester fibre materials
US4950304A (en) * 1987-10-02 1990-08-21 Ciba-Geigy Corporation Process for quenching or suppressing the fluorescence of substrates treated with fluorescent whitening agents
US4826978A (en) * 1987-12-29 1989-05-02 Milliken Research Corporation Reactive, non-yellowing triazine compounds useful as UV screening agents for polymers
US4962142A (en) * 1987-12-29 1990-10-09 Milliken Research Corporation Reactive, non-yellowing triazine compounds useful as UV screening agents for polymers
US5096489A (en) * 1989-08-25 1992-03-17 Ciba-Geigy Corporation Light-stabilized ink compositions
EP0434608A1 (en) * 1989-12-05 1991-06-26 Ciba-Geigy Ag Stabilized organic material
EP0442847A1 (en) * 1990-02-16 1991-08-21 Ciba-Geigy Ag Coating composition resistant to light, heat and acids
EP0444323A2 (en) * 1990-02-28 1991-09-04 Cytec Technology Corp. Stabilization of high solids coating with liquid compositions of triazine UV absorbers
US5106891A (en) * 1990-03-30 1992-04-21 Ciba-Geigy Corporation Light stabilized coating compositions containing a mixture of 2-hydroxyphenylbenzotriazole and 2-hydroxyphenyltriazine
EP0468921A1 (en) * 1990-07-23 1992-01-29 Ciba-Geigy Ag Aqueous dispersions of slightly soluble UV absorbing agents
EP0483488A1 (en) * 1990-10-29 1992-05-06 Cytec Technology Corp. Synergistic ultraviolet absorber compositions containing hydroxy aryl triazines and tetraalkyl piperidines
US5298067A (en) * 1991-02-21 1994-03-29 Ciba-Geigy Corporation Coating materials stabilized against light-induced degradation
GB2273498A (en) * 1992-12-03 1994-06-22 Ciba Geigy Ag S-Triazine UV absorbers

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013704A (en) * 1996-09-13 2000-01-11 Ciba Specialty Chemicals Corporation Hydroxyphenyltriazines
GB2317174B (en) * 1996-09-13 2000-05-17 Ciba Sc Holding Ag Hydroxyphenyltriazines
GB2317174A (en) * 1996-09-13 1998-03-18 Ciba Geigy Ag Hydroxyphenytriazine stabilisers
US6242597B1 (en) 1997-11-21 2001-06-05 Ciba Specialty Chemicals Corporation Trisaryl-1,3,5-triazine ultraviolet light absorbers
US6355708B2 (en) 1997-11-21 2002-03-12 Ciba Specialty Chemicals Corporation Trisaryl-1,3,5-triazine ultraviolet light absorbers
US6297377B1 (en) 1998-06-22 2001-10-02 Cytec Technology Corporation Benzocycle-substituted triazine and pyrimidine ultraviolet light absorbers
US6384113B1 (en) 1998-06-22 2002-05-07 Cytec Technology Corp. Benzocycle-substituted triazine and pyrimidine ultraviolet light absorbers
US6225468B1 (en) 1998-09-04 2001-05-01 Cytec Technology Corp. Process for making 2-(2,4,-dihydroxyphenyl) or 2-(2,4-dialkoxyphenyl)-4,6-bisaryl-1,3,5-triazines
US6486317B1 (en) 1998-09-04 2002-11-26 Ciba Specialty Chemicals Corporation Process for making 2-hydroxy-4-alkoxyphenyl or 2,4-dihydroxyphenyl substituted 1,3,5-triazine UV absorbers
US6486316B1 (en) 1998-11-17 2002-11-26 Cytec Technology Corp. Process for making triazine UV absorbers using Lewis acids and reaction promoters
US6710177B2 (en) 1998-11-17 2004-03-23 Cytec Technology Corp. Process for making triazine UV absorbers using Lewis acids and reaction promoters
US6730785B2 (en) 1998-11-17 2004-05-04 Cytec Technology Corp. Process for making triazine UV absorbers using lewis acids and reaction promoters
US6900314B2 (en) 1998-11-17 2005-05-31 Cytec Technology Corp. Process for making triazine UV absorbers using lewis acids and reaction promoters
WO2004076419A1 (en) 2003-02-26 2004-09-10 Ciba Specialty Chemicals Holding Inc. Water compatible sterically hindered alkoxyamines and hydroxy substituted alkoxyamines
EP2267523A2 (en) 2004-07-12 2010-12-29 Basf Se Stabilized electrochromic media
US20100062270A1 (en) * 2007-01-15 2010-03-11 Ciba Corporation Tinted clear coatings uv stabilized with 2-hydroxy phenyl triazine
US8399536B2 (en) 2007-06-29 2013-03-19 Basell Poliolefine Italia, s.r.l. Irradiated polyolefin composition comprising a non-phenolic stabilizer
EP2450401A1 (en) 2008-09-05 2012-05-09 THOR GmbH Flame-resistant compound containing a phosphoric acid derivative
WO2010072592A1 (en) 2008-12-22 2010-07-01 Basf Se Method of improving scratch resistance and related products and uses
US20120136098A1 (en) * 2009-07-29 2012-05-31 Fujifilm Corporation New triazine derivative, ultraviolet absorber, and resin composition
US8957140B2 (en) * 2009-07-29 2015-02-17 Fujifilm Corporation Triazine derivative, ultraviolet absorber, and resin composition
WO2015044785A2 (en) 2013-09-27 2015-04-02 Basf Se Polyolefin compositions for building materials
WO2015077635A2 (en) 2013-11-22 2015-05-28 Polnox Corporation Macromolecular antioxidants based on dual type moiety per molecule: structures methods of making and using the same
WO2017013028A1 (en) 2015-07-20 2017-01-26 Basf Se Flame retardant polyolefin articles

Also Published As

Publication number Publication date Type
US5684070A (en) 1997-11-04 grant
US5556973A (en) 1996-09-17 grant
JP3965603B2 (en) 2007-08-29 grant
DE69528331T2 (en) 2003-05-15 grant
EP0704437A3 (en) 1996-10-23 application
EP0704437A2 (en) 1996-04-03 application
CA2154626A1 (en) 1996-01-28 application
DE69528331D1 (en) 2002-10-31 grant
US5681955A (en) 1997-10-28 grant
US5675004A (en) 1997-10-07 grant
ES2181760T3 (en) 2003-03-01 grant
JPH0853427A (en) 1996-02-27 application
US5648488A (en) 1997-07-15 grant
US5637706A (en) 1997-06-10 grant
EP0704437B1 (en) 2002-09-25 grant

Similar Documents

Publication Publication Date Title
US4226763A (en) 2-[2-Hydroxy-3,5-di-(.alpha.,α-dimethylbenzyl)-phenyl]-2H-benzotriazole and stabilized compositions
US4278589A (en) 2-[2-Hydroxy-3,5-di-(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole and stabilized compositions
US4315848A (en) 2-[2-Hydroxy-3,5-di-(α,α-dimethylbenzyl)-phenyl]-2H-benzotriazole and stabilized compositions
US5216156A (en) Non-migrating 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine 1,3,5-triazine derivatives
EP0057160B1 (en) 2-(2-hydroxyphenyl)-benzotriazoles, their use as ultraviolet stabilizers and their preparation
US5145893A (en) Non-migrating 1-hydrocarbyloxy hindered amine derivatives as polymer stabilizers
US5679794A (en) Polymer stabilizers containing both hindered amine and hydroxylamine moieties
EP0309402A1 (en) N-substituted hindered amine stabilizers
US5021486A (en) Hindered amine-substituted malonic acid derivatives of s-triazine
US6537670B1 (en) Bis(alkyleneoxybenzophenone) ultraviolet light absorbers
US5844025A (en) 1,2-Bis-adducts of stable nitroxides with substituted ethylenes and stabilized compositions
US6344505B1 (en) Mono- and bis-benzotriazolyldihydroxybiaryl UV absorbers
US6271377B1 (en) Hydroxy-substituted N-alkoxy hindered amines and compositions stabilized therewith
US4972009A (en) Polymer stabilizers containing both hindered amine and nitrone moieties
US6867250B1 (en) Non-yellowing ortho-dialkyl aryl substituted triazine ultraviolet light absorbers
US6348591B1 (en) Red-shifted trisaryl-1,3,5-triazine ultraviolet light absorbers
EP0743309A1 (en) o-Hydroxyphenyl-s-triazines as UV stabilisers
WO1996028431A1 (en) Biphenyl-substituted triazines as light stabilizer
US5021478A (en) Compounds containing both UV-absorber and 1-hydrocarbyloxy hindered amine moieties and stabilized compositions
US6306939B1 (en) Poly-trisaryl-1,3,5-Triazine carbamate ultraviolet light absorbers
US4760148A (en) 5-aralkyl substituted 2H-benzotriazoles and stabilized compositions
US5280124A (en) 5-sulfonyl-substituted benzotriazole UV-absorbers
US6242597B1 (en) Trisaryl-1,3,5-triazine ultraviolet light absorbers
US5607987A (en) 2-(2-hydroxy-3-α cumyl-5-tert nonyl or dodecyl phenyl)-2H- Benzotriazole UV Absorbers
EP0698637A2 (en) Polyurethanes stabilized with selected 5-substituted benzotriazole UV absorbers

Legal Events

Date Code Title Description
FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12